Synthesis, Structure, and Properties of EuLnCuSe3 (Ln = Nd, Sm, Gd, Er)

EuLnCuSe3 (Ln = Nd, Sm, Gd, Er), due to their complex composition, should be considered new materials with the ability to purposefully change the properties. Samples of the EuLnCuSe3 were prepared using Cu, rare earth metal, Se (99.99%) by the ampoule method. The samples were obtained by the crystallization from a melt and annealed at temperatures 1073 and 1273 K. The EuErCuSe3 crystal structure was established using the single-crystal particle. EuErCuSe3 crystallizes in the orthorhombic system, space group Cmcm, KCuZrS3 structure type, with cell parameters a = 4.0555 (3), b = 13.3570 (9), and c = 10.4602 (7) Å, V = 566.62 (6) Å3. In structure EuErCuSe3, erbium ions are coordinated by selenium ions in the octahedral polyhedron, copper ions are in the tetrahedral coordination, europium ions are between copper and erbium polyhedra layers and are coordinated by selenium ions as two-cap trigonal prisms. The optical band gap is 1.79 eV. At 4.7 K, a transition from the ferrimagnetic state to the paramagnetic state was detected in EuErCuSe3. At 85 and 293 K, the compound is in a paramagnetic state. According to XRPD data, EuLnCuSe3 (Ln = Nd, Sm, Gd) compounds have a Pnma orthorhombic space group of the Eu2CuS3 structure type. For EuSmCuSe3, a = 10.75704 (15) Å, b = 4.11120 (5) Å, c = 13.37778 (22) Å. In the series of EuLnCuSe3 compounds, the optical band gap increases 1.58 eV (Nd), 1.58 eV (Sm), 1.72 eV (Gd), 1.79 eV (Er), the microhardness of the 205 (Nd), 210 (Sm), 225 (Gd) 235 ± 4 HV (Er) phases increases, and the thermal stability of the phases increases significantly. According to the measurement data of differential scanning calorimetry, the EuNdCuSe3 decomposes, according to the solid-phase reaction T = 1296 K, ΔH = 8.2 ± 0.8 kJ/mol. EuSmCuSe3 melts incongruently T = 1449 K, ΔH = 18.8 ± 1.9 kJ/mol. For the EuGdCuSe3, two (Tα↔β = 1494 K, ΔHα↔β = 14.8 kJ/mol, Tβ↔γ = 1530 K, ΔHβ↔γ = 4.8 kJ/mol) and for EuErCuSe3 three polymorphic transitions (Tα↔β = 1561 K, ΔHα↔β = 30.3 kJ/mol, Tβ↔γ = 1579 K, ΔHβ↔γ = 4.4 kJ/mol, and Tγ↔δ = 1600 K, ΔHγ↔δ = 10.1 kJ/mol). The compounds melt incongruently at the temperature of 1588 K, ΔHmelt = 17.9 ± 1.8 kJ/mol and 1664 K, ΔHmelt = 25.6 ± 2.5 kJ/mol, respectively. Incongruent melting of the phases proceeds with the formation of a solid solution of EuSe and a liquid phase.

Red Carbon: a Carbon-Oxygen-based covalent semiconductor for selective amine sensing

The requirements for organic semiconductor materials and new methods for their synthesis at low temperature have risen over the last decades, especially due to concerns of sustainability. Herein, we present an innovative method for the synthesis of a so-called “red carbon” thin film, being composed of carbon and oxygen, only. This material was already described by Kappe and Ziegler at the beginning of the 20th century, but now can complement the current research on covalent organic semiconductor materials. The herein described red carbon can be homogeneous deposited on glass substrates as thin ilms which reveal a highly ordered structure. The films are highly reactive towards amines and were employed as amine vapor sensors for a scope of analogous amines. The gas-to-solid phase reaction causes a significant change of the films optical properties in all cases, blue-shifting the bandgap and the photoluminescence spectra from the red to the near UV range. The irreversible chemical reaction between the thin film and the vapor was also exploited for the preparation of nitrogen containing thin carbon films. We expect the herein presented red carbon material is of interest not only for sensing applications, but also in optoelectronics.

STUDY OF TECHNICAL CELLULOSE AS A MATRIX-SORBENT TO DEVELOP EXPRESS ANALYTIC SYSTEM FOR WATER SAFETY CONTROL

The study presented by the authors is devoted to the study of the properties and the possibility of using technical cellulose from non-wood plant raw materials as a solid-phase matrix to obtain solid-phase reactive indicator systems by the following methods: synthesis method on the base of a hetarylformazane immobilized on a cellulose matrix and development of analytical systems based on preconcentration of the determined metal ion by a matrix with subsequent its «revealing» by the formazan («revealing» method). The article focuses on determination of optimal combinations of chromogenic organic reagents (hetarylformazanes) and cellulose-based matrices for developing solid-phase reaction-based indicator systems. Adsorption features of formazan reagents onto cellulose matrices was studied. It has been established the relation between the reagent molecule structure, composition of cellulose matrix and analytical properties of the test-systems synthesized to determine metal ions. Different approaches were developed and applied to reveal the visually observable and easily measured effect due to cellulose properties as well as properties of hetarylformazanes fixed on the surface of the matrix. This fact allows to control sensitivity and selectivity of solid-phase reactive indicator systems for water quality assessment.

Preparation of complex oxide (Pr0.8Y0.2)0.6Ca0.4CoO3 from Pr–Y–Ca–Co gel synthesized by ultrasonic irradiation and its metal-insulator transition characteristics

We previously reported that a swollen gel possessing a uniform composition and prolonged stability can be conveniently prepared by simple ultrasonic irradiation of an ethanol suspension of calcium acetate, which is poorly soluble in ethanol. In this study, the same gel synthesis method was applied to prepare the multicomponent oxide (Pr1−yYy)1−xCaxCoO3 (PYCCO), which undergoes a metal-insulator phase transition. Calcination of the Pr–Y–Ca–Co swollen gel at 800 °C for 12 h in air afforded PYCCO nanoparticles with good crystallinity, representing a faster and more convenient route compared with conventional solid-phase reaction methods or sol–gel methods.

Features of structure, magnetic state and electrodynamic performance of SrFe12−xInxO19

Indium-substituted strontium hexaferrites were prepared by the conventional solid-phase reaction method. Neutron diffraction patterns were obtained at room temperature and analyzed using the Rietveld methods. A linear dependence of the unit cell parameters is found. In3+ cations are located mainly in octahedral positions of 4fVI and 12 k. The average crystallite size varies within 0.84–0.65 μm. With increasing substitution, the TC Curie temperature decreases monotonically down to ~ 520 K. ZFC and FC measurements showed a frustrated state. Upon substitution, the average and maximum sizes of ferrimagnetic clusters change in the opposite direction. The Mr remanent magnetization decreases down to ~ 20.2 emu/g at room temperature. The Ms spontaneous magnetization and the keff effective magnetocrystalline anisotropy constant are determined. With increasing substitution, the maximum of the ε/ real part of permittivity decreases in magnitude from ~ 3.3 to ~ 1.9 and shifts towards low frequencies from ~ 45.5 GHz to ~ 37.4 GHz. The maximum of the tg(α) dielectric loss tangent decreases from ~ 1.0 to ~ 0.7 and shifts towards low frequencies from ~ 40.6 GHz to ~ 37.3 GHz. The low-frequency maximum of the μ/ real part of permeability decreases from ~ 1.8 to ~ 0.9 and slightly shifts towards high frequencies up to ~ 34.7 GHz. The maximum of the tg(δ) magnetic loss tangent decreases from ~ 0.7 to ~ 0.5 and shifts slightly towards low frequencies from ~ 40.5 GHz to ~ 37.7 GHz. The discussion of microwave properties is based on the saturation magnetization, natural ferromagnetic resonance and dielectric polarization types.

Crystal Structure and Magnetism of Potassium-Intercalated 2,7-Dimethylnaphthalene

The rich physical properties of metal-intercalated polycyclic aromatic hydrocarbon materials have recently attracted considerable attention. Crystals of potassium-intercalated 2,7-dimethylnaphthalene were synthesized via solid phase reaction. The combination of XRD measurements and first-principles calculations indicated that each unit cell contains two potassium atoms and four organic molecules. Magnetization measurements revealed that the samples show a Curie paramagnetism. Theoretical calculations showed that the intercalated structure becomes metallic and has local magnetic moment. Raman spectroscopy confirmed the migration of electron from potassium 4s to carbon 2p orbital, which is the source of magnetism. Our research on naphthalene derivatives is helpful for expanding the range of novel organic magnetic materials and organic superconducting materials.