Search Results (49)

Composite materials based on low-density polyethylene (LDPE) embedded with iron-manganese nanoparticles with compositions Fe_0.9Mn_0.1 and Fe_0.8Mn_0.2 were prepared and investigated. The newly created composites were characterized using transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and Mössbauer spectroscopy. The composition, electronic, and atomic structure of the nanoparticles were established. The study confirms that the nanoparticles possess a ‘core-shell’ structure, the nature of which depends on the manganese content. The nanoparticles of Fe_0.8Mn_0.2 in LDPE exhibit a three-layered structure: a metallic α-Fe core is coated with an intermediate oxidized layer structurally close to Fe₂O₃, while the outermost shell consists of manganese oxide (Mn₂O₃). In contrast, nanoparticles with lower Mn content Fe_0.9Mn_0.1 show a predominantly fully oxidized structure. This structural evolution is consistent with thermodynamic principles, where manganese, having a higher oxide formation enthalpy, migrates to the surface. The core–shell architecture is promising for applications requiring stable magnetic components or tailored catalytic interfaces within a polymer matrix. Full article

High-efficiency diesel and lean-burn engines produce lower exhaust temperatures, which can delay the activation of after-treatment catalysts such as Diesel Oxidation Catalysts (DOCs). This study explores ion beam sputtering as a post-synthesis strategy to enhance the low-temperature activity of commercial Pt/CeO₂–ZrO₂ catalysts. Low-energy ions (0.5–1.5 keV) were applied with controlled variations in treatment number, beam current, and exposure time to selectively generate oxygen vacancies and improve Pt dispersion. Structural and chemical effects were characterized using X-ray diffraction (XRD), BET surface area measurements, X-ray photoelectron spectroscopy (XPS) and extended X-ray absorption fine structure (EXAFS). Catalytic performance was evaluated through CO and C₃H₆ oxidation under conditions mimicking lean-burn engine exhaust. Increasing the number of ion treatments progressively lowered light-off temperatures, correlating with enhanced Pt–Ce³⁺ interactions and improved surface reducibility. Variations in beam current and exposure time further modulated these surface effects, confirming the tunable nature of the approach. The results demonstrate that ion beam sputtering selectively modifies the catalyst surface without altering the bulk structure, directly linking atomic-scale modifications to improved low-temperature activity. This strategy offers a promising route to overcome delayed light-off issues in modern high-efficiency engines, providing a precise, controllable method to optimize emission control catalysts. Full article

X-ray absorption spectroscopy (XAS) and X-ray emission spectroscopy (XES) are analytical techniques enabling precise analysis of the electronic structure and local atomic environment in chemical compounds and materials. Their application spans materials science, chemistry, biology, and environmental sciences, supporting studies on catalytic mechanisms, redox processes, and metal speciation. A key advantage of both techniques is element selectivity, allowing the analysis of specific elements without matrix interference. Their high sensitivity to chemical state and coordination enables determination of oxidation states, electronic configuration, and local geometry. These methods are applicable to solids, liquids, and gases without special sample preparation. Modern XAS and XES studies are typically performed using synchrotron radiation, which provides an intense, monochromatic X-ray source and allows advanced in situ and operando experiments. Sub-techniques such as XANES (X-ray absorption near-edge structure), EXAFS (Extended X-ray Absorption Fine Structure), and RIXS (resonant inelastic X-ray scattering) offer enhanced insights into oxidation states, local structure, and electronic excitations. Despite their broad scientific use, applications in pharmaceutical research remain limited. Nevertheless, recent studies highlight their potential in analyzing crystalline active pharmaceutical ingredients (APIs), drug–biomolecule interactions, and differences in drug activity. This review introduces the fundamental aspects of XAS and XES, with an emphasis on practical considerations for pharmaceutical applications, including experimental design and basic spectral interpretation. Full article

Complex oxides with the general formula Gd₂(Ti_1−xZr_x)₂O₇ are promising candidates for radioactive waste immobilization due to their capacity to withstand radiation by dissipating part of the free energy driving defect creation and phase transitions. In this study, samples with varying zirconium content (xZr = 0.00, 0.15, 0.25, 0.375, 0.56, 0.75, 0.85, 1.00) were synthesized via the sol–gel method and thermally treated at 500 °C to obtain nanosized powders mimicking the defective structure of irradiated materials. Synchrotron-based techniques were employed to investigate their structural properties: High-Resolution X-ray Powder Diffraction (HR-XRPD) was used to assess long-range structure, while Pair Distribution Function (PDF) analysis and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy provided insights into the local structure. HR-XRPD data revealed that samples with low Zr content (xZr ≤ 0.25) are amorphous. Increasing Zr concentration led to the emergence of a crystalline phase identified as defective fluorite (xZr = 0.375, 0.56). Samples with the highest Zr content (xZr ≥ 0.75) were fully crystalline and exhibited only the fluorite phase. The experimental G(r) functions of the fully crystalline samples in the low r range are suitably fitted by the Weberite structure, mapping the relaxations induced by structural disorder in defective fluorite. These structural insights informed the subsequent EXAFS analysis at the Zr-K and Gd-L₃ edges, confirming the splitting of the cation–cation distances associated with different metal species. Moreover, EXAFS provided a local structural description of the amorphous phases, identifying a consistent Gd-O distance across all compositions. Full article

The nanostructural features of a mechanically alloyed Sb-doped (Ti_0.4Zr_0.6)_0.7Hf_0.3NiSn thermoelectric (TE) Half-Heusler (HH) compound were addressed using Transmission Electron Microscopy (TEM) coupled with Energy Dispersive Spectroscopy measurements and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. The EXAFS measurements at the Ni-K, Sn-K, Zr-K, and Hf-L₃-edge were implemented in an effort to reveal the influence of Hf and Zr incorporation into the crystal with respect to their previously measured TE properties. The substitution of Ti by Hf and Zr is expected to yield local lattice distortions due to the different atomic sizes of the dopants or/and electronic charge redistribution amongst the cations. However, the material is characterised by a high degree of crystallinity in both the short and long-range order, on average, and the nominal stoichiometry is identified as (Zr_0.42Hf_0.30Ti_0.28)NiSn_0.98Sb_0.02. The synergistic effect of minimization of extended structural defects or lattice distortions and considerable alloying-induced point defect population contributes to the improved TE properties and leads to the previously reported enhancement of the figure of merit of the mixed HHs. Full article

Ce₂Pt₆Ga₁₅ is a heavy fermion compound near the quantum critical point (QCP). Its crystal structure may exhibit magnetic frustration due to a honeycomb arrangement; however, stacking faults in the crystal hinder structural analysis. As a local structure probe, extended X-ray absorption fine structure (EXAFS) is less sensitive to stacking faults and is a powerful tool for crystal structure determination. We synthesized single-crystal Ce₂Pt₆Ga₁₅, performed single-crystal and powder X-ray diffraction experiments, and conducted X-ray absorption spectroscopy (XAS) measurements. The composition of Ce₂Pt₆Ga₁₅ deviates from stoichiometry, suggesting Ce and Ga enrichment or Pt site deficiencies. A comparison of X-ray absorption near-edge structure (XANES) at the Ce L₃-edge with reference materials suggests that Ce valence is likely trivalent. To determine the exact structure, we simultaneously analyzed EXAFS spectra at the Ce L₃-, Pt L₃-, and Ga K-edges. The EXAFS spectra of Ce₂Pt₆Ga₁₅ are inconsistent with the hexagonal Sc_0.6Fe₂Si_4.9-type structure but are better explained by an orthorhombic structure with a honeycomb arrangement. Full article

This study explores the phase composition, local atomic structure, and magnetic properties of biogenic nanomaterials synthesized through microbially mediated biomineralization by the sulfate-reducing bacterium Desulfovibrio species strain A2 (Cupidesulfovibrio). Using X-ray diffraction (XRD), transmission electron microscopy (TEM), Mössbauer spectroscopy, X-ray absorption near-edge structure (XANES) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and magnetic measurements, we identified a mixture of vivianite (Fe₃(PO₄)₂·8H₂O) and sulfur-containing crystalline phases (α-sulfur). XRD analysis confirmed that the vivianite phase, with a monoclinic I2/m structure, constitutes 44% of the sample, while sulfur-containing phases (α-sulfur, Fddd) account for 56%, likely as a result of bacterial sulfate-reducing activity. X-ray absorption spectroscopy (XAS) and EXAFS revealed the presence of multiple sulfur oxidation states, including elemental sulfur and sulfate (S⁶⁺), underscoring the role of sulfur in the sample’s structure. Mössbauer spectroscopy identified the presence of ferrihydrite nanoparticles with a blocking temperature of approximately 45 K. Magnetic measurements revealed significant coercivity (~2 kOe) at 4.2 K, attributed to the blocked ferrihydrite nanoparticles. The results provide new insights into the structural and magnetic properties of these microbially mediated biogenic nanomaterials, highlighting their potential applications in magnetic-based technologies. Full article

We have investigated the effect of the Ni substitution on the local structure and the valence electronic states of the ${\mathrm{SrFe}}_{2-x}$${\mathrm{Ni}}_x$${\mathrm{As}}_2$ (x = 0.00, 0.16, and 0.23) superconductor with a multi-edge extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopy. The As K-edge and Fe K-edge EXAFS measurements in the two polarizations (E‖ab and E‖c) show a clear change in the local structure with Ni concentration. The near-neighbor bondlengths and the related mean-square relative displacements (MSRDs) decrease as the Ni content increases. The polarized XANES spectra at the As, Fe and Ni K edges reveal a systematic change in the anisotropy of the valence electronic structure. The results suggest that the quasi 2D electronic structure of this system tends to become more isotropic as the Ni content increases. The local structure and the valence electronic states are discussed in the frame of the evolving electronic transport of the ${\mathrm{SrFe}}_{2-x}$${\mathrm{Ni}}_x$${\mathrm{As}}_2$ system. Full article

Silica-supported chromium oxide catalysts, also named Phillips chromium catalysts (PCCs), provide more than half of the world’s production of high- and medium-density polyethylenes. PCCs are usually prepared in the Cr(VI)/SiO₂ form, which is subjected to reductive activation. It has been explicitly proven that CO reduces Cr(VI) to Cr(II) species that initiate ethylene polymerization; ethylene activates Cr(VI) sites as well, but the nature of the catalytic species is complicated by the presence of the ethylene oxidation products. It is widely accepted that the catalytic species are of a Cr(III)–alkyl nature, but this common assumption faces the challenge of “extra” hydrogen: the formation of similar species under the action of even-electron reducing agents requires an additional H atom. Relatively recently, it was found that saturated hydrocarbons can also activate CrO_x/SiO₂, and alkyl fragments turn out to be bonded with a polyethylene chain. In recent years, there have been numerous experimental and theoretical studies of the structure and chemistry of PCCs at the different stages of preparation and activation. The use of modern spectral methods (such as extended X-ray absorption fine structure (EXAFS), X-ray absorption near-edge structure (XANES), and others); operando IR, UV–vis, EPR, and XAS spectroscopies; and theoretical approaches (DFT modeling, machine learning) clarified many essential aspects of the mechanisms of CrO_x/SiO₂ activation and catalytic behavior. Overall, the Cosse–Arlman mechanism of polymerization on Cr(III)–alkyl centers is confirmed in many works, but its theoretical support required the development of nontrivial and contentious mechanistic concepts of Cr(VI)/SiO₂ or Cr(II)/SiO₂ activation. On the other hand, conflicting experimental data continue to be obtained, and certain mechanistic concepts are being developed with the use of outdated models. Strictly speaking, the main question of what type of catalytic species, Cr(II), Cr(III), or Cr(IV), comes into polymerization still has not received an unambiguous answer. The role of the chemical nature of the support—through the prism of the nature, geometry, and distribution of the active sites—is also not clear in depth. In the present review, we endeavored to summarize and discuss the recent studies in the field of the preparation, activation, and action of PCCs, with a focus on existing contradictions in the interpretation of the experimental and theoretical results. Full article

Rhenium (Re) is an extremely rare element, with a crustal abundance of approximately 0.4 parts per billion (ppb) and a sea water concentration of 8.3 parts per trillion (ppt). However, Re concentrations in anoxic marine sediments range from 2 to 184 ppb, which is attributed to reduction of the highly soluble perrhenate ion (Re(VII)O₄⁻) to insoluble Re(IV) species. Anoxic sediments typically contain Fe(II) and sulfide species, which could potentially reduce Re(VII) to Re(IV). In this study, we examined the interactions of KReO₄ with magnetite (Fe₃O₄), siderite (FeCO₃), vivianite (Fe₃(PO₄)₂•8H₂O), green rust (mixed Fe(II)/Fe(III) layered double hydroxide), mackinawite (FeS), and chemically reduced nontronite (NAu-1) using X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy to determine the valence state and speciation of Re. Uptake of Re by green rust was rapid, with ~50% associated with the solids within 2 days. In contrast, there was <10% uptake by the other Fe(II) phases over 48 days. Reduction of Re(VII) to Re(IV) was only observed in the presence of green rust, producing clusters of bidentate-coordinated Re(IV)O₆ octahedra.. These results suggest that except for green rust, the potential for other Fe(II)-bearing minerals to act as reductants for ReO₄⁻ in sedimentary environments requires further investigation. Full article

Currently, electrically conductive polymers based on transition metal complexes [M(Salen)], as well as their composites, are among the systems showing promise as catalysts, electrochromic and electroluminescent materials, and electrodes for energy storage (for batteries and supercapacitors). The current review focuses on elucidating the atomic and electronic structure of metal–salen complexes, their polymers, and composites with nanostructured carbon (carbon nanotubes and graphene) using modern X-ray spectroscopy methods (X-ray photoelectron (XPS) and valence-band photoemission (VB PES) spectroscopy, as well as near-edge (NEXAFS) and extended (EXAFS) X-ray absorption fine structure spectroscopy). We trust that this review will be of valuable assistance to researchers working in the field of synthesizing and characterizing metal–salen complexes and composites based on them. Full article

Future space missions to Mars will depend on the development of bioregenerative life support systems. Mars regolith contains most of the nutrients needed for plant growth, but not organic matter (OM). Although Mars simulants have been deeply characterized and tested as growing media, no data are available about their possible modification occurring during terraforming, including the interaction of exogeneous OM with iron (Fe) oxides, particularly abundant in Mars regolith. The aim of this study was to investigate the mineral transformation and the OM evolution occurring in the early stages of the terraforming process. Potato was grown for 99 days on Mojave Mars Simulant MMS-1, alone (R100) and mixed with a compost 70:30 v:v (R70C30), and on a fluvial sand, alone (S100) and mixed with compost (S70C30), for comparison. Bulk (BK) and potato tubero/rhizo-sphere (RH) soils were fractionated to obtain particulate OM (POM) and mineral-associated OM (MAOM). Bulk samples and corresponding fractions were characterized for total nitrogen and organic carbon (C) and analyzed by Fe K-edge X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy. Organic C increased by 10 and 25 times in S70C30 and R70C30, respectively, compared to S100 and R100. Most of the organic C accumulated in the POM fraction of both growing substrates, while its content in the MAOM was 3 times higher in R70C30 than in S70C30. No significant differences between BK and RH were found. Finally, ferrihydrite mediated exogenous OM stabilization in regolith-based substrates, while Fe(III)-OM complexes were detected exclusively in sand-based growing media. Understanding mechanisms and testing potential sustainable practices for creating Mars regolith similar to terrestrial soil will be fundamental to sustain food crop production on Mars. Full article

The flux growth of InVO₄ bulk single crystals has been explored for the first time. The reported eutectic composition at a ratio of V₂O₅:InVO₄ = 1:1 could not be used as a self-flux since no sign of melting was observed up to 1100 °C. Crystals of InVO₄ of typical size 0.5 × 1 × 7 mm³ were obtained using copper pyrovanadate (Cu₂V₂O₇) as a flux, using Pt crucibles. X-ray powder diffraction confirmed the orthorhombic Cmcm structure. Rests of the flux material were observed on the sample surface, with occasional traces of Pt indicating some level of reaction with the crucible. X-ray absorption spectroscopy showed that oxidation states of indium and vanadium ions are +3 and +5, respectively. The size and high quality of the obtained InVO₄ crystals makes them excellent candidates for further study of their physical properties. Full article

It is known that doping zinc sulfide (ZnS) nanoparticles with Mn or Cu ions significantly affects their luminescent properties. Herein, we investigated how dopant atoms are incorporated into the structure of ZnS using X-ray diffraction and multi-edge X-ray absorption spectroscopy. The observed broadening of the X-ray diffraction patterns indicates an average crystallite size of about 6 nm. By analyzing the Zn, Mn, and Cu K-edge extended X-ray absorption fine structure (EXAFS) spectra using the reverse Monte Carlo method, we were able to determine the relaxations of the local environments around the dopants. Our findings suggested that upon the substitution of Zn by Mn or Cu ions, there is a shortening of the Cu–S bonds by 0.08 Å, whereas the Mn–S bonds exhibited lengthening by 0.07 Å. These experimental results were further confirmed by first-principles density functional theory calculations, which explained the increase in the Mn–S bond lengths due to the high-spin state of Mn${}^{2+}$ ions. Full article

New coordination compounds of copper(II) with 2,5-bis(ethylthio)-1,3,4-thiadiazole (L¹) and 2,5-bis(pyridylmethylthio)-1,3,4-thiadiazole (L²) with compositions Cu(L¹)₂Br₂, Cu(L¹)(C₂N₃)₂, Cu(L²)Cl₂, and Cu(L²)Br₂ were prepared. The complexes were identified and studied by CHN analysis, infrared (IR) spectroscopy, powder X-Ray diffraction (XRD), and static magnetic susceptibility. The crystal structures of Cu(II) complexes with L¹ were determined. The structures of the coordination core of complexes Cu(L²)Cl₂ and Cu(L²)Br₂ were determined by Extended X-ray absorption fine structure (EXAFS) spectroscopy. Magnetization measurements have revealed various magnetic states in the studied complexes, ranging from an almost ideal paramagnet in Cu(L¹)₂Br₂ to alternating-exchange antiferromagnetic chains in Cu(L¹)(C₂N₃)₂, where double dicyanamide bridges provide an unusually strong exchange interaction (J₁/k_B ≈ −23.5 K; J₂/k_B ≈ −20.2 K) between Cu(II) ions. The cytotoxic activity of copper(II) complexes with L² was estimated on the human cell lines of breast adenocarcinoma (MCF-7) and hepatocellular carcinoma (HepG2). Full article