Cooperative Large-Hysteresis Spin-Crossover Transition in the Iron(II) Triazolate [Fe(ta)2] Metal-Organic Framework.

The metal-organic framework [Fe(ta)2] (Hta = 1H-1,2,3-triazole) containing Fe(II) ions and 1,2,3-triazolate ligands shows a reversible phase transition while retaining the cubic crystal symmetry and space group Fd3m (no. 227). The phase transition between room temperature (RT-[Fe(ta)2]; a = 16.6315(2) Å, V = 4600.39(8) Å3) and high temperature (HT-[Fe(ta)2]; a = 17.7566(4) Å, V = 5598.6(1) Å3) phases occurs at a temperature above 290 °C, whereas the phase transition between HT- and RT-[Fe(ta)2] starts at a temperature below 210 °C. Both [Fe(ta)2] polymorphs have identical bond topologies, but they differ by a large increase of the unit cell's volume of 22% for HT-[Fe(ta)2]. The compounds are characterized by powder X-ray diffraction, differential scanning calorimetry, and thermogravimetric analyses. Additionally, Mössbauer spectroscopy, magnetic studies, and the electronic structure of both phases are discussed in detail with respect to the spin-crossover transition from the low-spin (RT-[Fe(ta)2]) to the high-spin phase (HT-[Fe(ta)2]).

Formation, Microstructure, and Properties of Dissimilar Welded Joint between CrMnFeCoNi and Fe.

This research explores the welding process of a high-entropy CrMnFeCoNi alloy with iron, unraveling the intricate chemical compositions that materialize in distinct regions of the weld joint. A mid-wave infrared thermal camera was deployed to monitor the cooling sequences during welding. A thorough analysis of the metallographic sample from the weld joint, along with measurements taken using a nano-hardness indenter, provided insights into the hardness and Young's modulus. The element distribution across the weld joint was assessed using a scanning electron microscope equipped with an EDS spectrometer. Advanced techniques such as X-ray diffraction and Mössbauer spectroscopy underscored the prevalence of the martensitic phase within the weld joint, accompanied by the presence of bcc (iron) and fcc phases. In contrast, Young's modulus in the base metal areas displayed typical values for a high-entropy alloy (202 GPa) and iron (204 GPa). The weld joint material displayed substantial chemical heterogeneity, leading to noticeable concentration gradients of individual elements. The higher hardness noted in the weld (up to 420 HV), when compared to the base metal regions (up to 290 HV for CrMnFeCoNi alloy and approximately 150 HV for iron), can be ascribed to the dominance of the martensitic phase. These findings provide valuable insights for scenarios involving diverse welded joints containing high-entropy alloys, contributing to our understanding of materials engineering.

Surface modification of magnetic nanoparticles by bacteriophages and ionic liquids precursors.

Magnetic nanoparticles (MNPs) have recently been a point of interest for many researchers due to their properties. However, the studies on the influence of bacteriophages on the synthesis of MNPs seem to be lacking. Furthermore, bacteriophage-modified MNPs have not been combined with n-alkyl quaternary ammonium ionic liquid precursors (QAS). In this study, the aim was to assess the influence of two distinctly different bacteriophages (Escherichia phage P1 and Pseudomonas phage Φ6) on MNPs synthesis in the presence or absence of QAS. Synthesized MNPs have been characterized with X-ray diffraction (XRD) and Mössbauer spectroscopy in terms of changes in the crystallographic structure; scanning electron microscopy (SEM) for changes in the morphology; and ζ-potential. Moreover, the sorption parameters and the loss of viability of bacteria that interacted with MNPs have been determined. The sorption of bacteria differs significantly among the tested samples. Furthermore, the viability of the bacteria adsorbed on MNPs varies in the presence of QAS, depending on the length of the n-alkyl chain. The study has revealed that MNPs can be bound with bacteriophages. Mössbauer spectroscopy has also revealed the probable influence of bacteriophages on the formation of crystals. However, these phenomena require further studies.

Non-redox reactivity of V(II) and Fe(II) formamidinates towards CO2 resulting in the formation of novel M(II) carbamates.

Chemical fixation of CO2 is a powerful tool for the preparation of novel multinuclear metal complexes and functional materials. Particularly, the insertion of CO2 into a metal-X bond (X = H, C, N, O) often is a key elementary step in the various processes transforming this greenhouse gas into valuable products. Herein, we report on the reactivity between CO2 and V(II) and Fe(II) complexes supported by N,N'-bis(2,6-diisopropylphenyl)formamidinate ligands (DippF). The reactions proceeded with multiple insertions of CO2 into the M-N bonds leading to the isolation of three novel complexes: [(κ2-DippFCO2)(THF)V(µ-DippFCO2)3V(THF)], [(κ2-DippFCO2)Fe(µ-DippFCO2)2(µ-DippF)Fe(THF)] and [(κ2-DippFCO2)Fe(µ-DippFCO2)3Fe(κ1-DippFH)], which were characterised using single-crystal X-ray diffraction, FTIR and 57Fe Mössbauer spectroscopy (for the diiron compounds). We provide the first well-documented studies of the CO2 reactivity towards the V-N bond and broaden the state-of-the-art of the undeveloped area of the reactivity of low-valent V(II) complexes. Moreover, we showed that the effectivity of the examined CO2 insertion processes strongly depends on the used solvent's characteristics (for the Fe(II) system) and the metal centre's coordination sphere geometry (for the V(II) system).

A new iron-phosphate compound (Fe7P11O38) obtained by pyrophosphate stoichiometric glass devitrification.

Iron phosphates are a wide group of compounds that possess versatile applications. Their properties are strongly dependent on the role and position of iron in their structure. Iron, because of its chemical character, is able to easily change its redox state and accommodate different chemical surroundings. Thus, iron-phosphate crystallography is relatively complex. In addition, the compounds possess intriguing magnetic and electric properties. In this paper, we present crystal structure properties of a newly developed iron-phosphate compound that was obtained by devitrification from iron-phosphate glass of pyrophosphate stoichiometry. Based on X-ray diffraction (XRD) studies, the new compound (Fe7P11O38) was shown to adopt the hexagonal space group P63 (No. 173) in which iron is present as Fe3+ in two inequivalent octahedral and one tetrahedral positions. The results were confirmed by Raman and Mössbauer spectroscopies, and appropriate band positions, as well as hyperfine interaction parameters, are assigned and discussed. The magnetic and electric properties of the compound were predicted by ab initio simulations. It was observed that iron magnetic moments are coupled antiferromagnetically and that the total magnetic moment of the unit cell has an integer value of 2 µB. Electronic band structure calculations showed that the material has half-metallic properties.

The influence of acid treatments over vermiculite based material as adsorbent for cationic textile dyestuffs.

The influence of different acid treatments over vermiculite was evaluated. Equilibrium, kinetic and column studies have been conducted. The results showed that vermiculite first treated with nitric acid and then with citric acid has higher adsorption capacity, presenting maximum adsorption capacities in column experiments: for Astrazon Red (AR), 100.8 ± 0.8 mg g(-1) and 54 ± 1 mg g(-1) for modified and raw material, respectively; for Methylene Blue (MB) 150 ± 4 mg g(-1) and 55 ± 2 mg g(-1) for modified and raw material, respectively. Materials characterization by X-ray diffraction, UV-vis-diffuse reflectance spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy, X-ray fluorescence, N2 adsorption and CEC determination, has been performed. The results suggest the existence of exchange of interlayer cations, leaching of metals from vermiculite's sheets and formation of an amorphous phase in the material. Adsorption follows pseudo 2(nd) order model kinetics for both dyestuffs and equilibrium occurs accordingly to Langmuir's model for AR and Freundlich's model for MB. In column systems Yan's model is the best fit. The enhanced properties of acid treated vermiculite offer new perspectives for the use of this adsorbent in wastewater treatment.