Solids, Volume 5, Issue 2 (June 2024) – 11 articles

Here, we present the synthesis of a novel quaternary compound, iodide carbonate Na₅(CO₃)₂I, at 18(1) and 25.1(5) GPa in laser-heated diamond anvil cells. Single-crystal synchrotron X-ray diffraction provides accurate structural data for Na₅(CO₃)₂I and shows that the structure of the material can be described as built of INa₈ square prisms, distorted NaO₆ octahedra, and trigonal planar CO₃²⁻ units. Decompression experiments show that the novel iodide carbonate is recoverable in the N₂ atmosphere to ambient conditions. Our ab initio calculations agree well with the experimental structural data, provide the equation of state, and shed light on the chemical bonding and electronic properties of the new compound. Full article

We report angle-resolved energy spectra of electron emitted in the interaction of slow singly charged heavy ions with Mg surface. The work is focused mainly on the excitation of plasmons of Mg under Argon impact. Potential excitation of plasmons occurs when incoming ions are neutralized at the expense of the potential energy carried by incoming ions. The process competes with the known mechanisms of neutralization via Auger transitions. Differently from Al samples, our results show that the neutralization of Ar⁺ ions at Mg is dominated by the excitation of surface plasmons by the potential energy released in the electron capture process that neutralizes incoming ions. Bulk plasmon excitation is observed at higher impact energy and is ascribed to fast electrons excited by the transfer of the kinetic energy of incoming particles. The data show that bulk plasmon excitation occur inside the bulk, while the theoretically predicted excitation by potential energy transfer of incoming projectiles is not observed. Full article

Phase equilibria studies were performed in the Li₂O-SiO₂ system for heat-treated samples using Scanning Electron Microscope (SEM) and X-Ray Diffraction (XRD). The temperature of the eutectic reaction (Liq. ⇌ Li₄SiO₄ + Li₂SiO₃) was experimentally determined at 1289 K using Differential Thermal Analysis (DTA). No evidences of the Li₆Si₂O₇ formation was found by the experimental investigation and therefore, it was not considered. Heat capacity of the Li₈SiO₆ phase was measured using Differential Scanning Calorimetry (DSC). Solid phases of the Li₂O-SiO₂ system were described as stoichiometric compounds and liquid phases by two-sublattice partially ionic liquid model. Four stoichiometric intermediate compounds were considered to be stable (Li₈SiO₆, Li₄SiO₄, Li₂SiO₃ and Li₂Si₂O₅). The polymorphic transformation in Li₂Si₂O₅ phase was accounted and the metastable liquid miscibility gap on SiO₂-rich side was reproduced. The calculated phase diagram satisfactorily agrees with the experimental phase equilibria as well as calculated thermodynamic properties reproduces experimental values within uncertainty limits. Full article

The disadvantage of chalcogenide glasses containing rare earth ions as luminescent materials for the IR optical range is the strong concentration quenching of luminescence due to the non-uniform distribution of rare earth ions in the glass matrix. This study investigates the effect of grinding chalcogenide glass containing Pr³⁺ ions in a planetary ball mill on its luminescent properties in the near-IR range, as well as its optical properties and structure. The results indicate that milling, under certain conditions, leads to a decrease in the concentration quenching of the luminescence of Pr³⁺ ions. This finding suggests that milling can be used in the development of glassy materials with the increased efficiency of luminescence of rare earth ions. However, it is essential to consider that high-energy milling may result in the formation of areas with increased pressure in the obtained material, leading to structural changes in the glass. Full article

Due to its large hole mobility, organic rubrene (C₄₂H₂₈) has attracted research questions regarding its applications in electronic devices. In this work, extensive first-principles calculations are performed to predict some temperature- and doping-dependent properties of organic semiconductor rubrene. We use density functional theory (DFT) to investigate the electronic structure, elastic and transport properties of the orthorhombic phase of the rubrene compound. The calculated band structure shows that the orthorhombic phase has a direct bandgap of 1.26 eV. From the Vickers hardness (1.080 GPa), our calculations show that orthorhombic rubrene is not a super hard material and can find useful application as a flexible semiconductor. The calculated transport inverse effective mass and electronic fitness function show that the orthorhombic rubrene crystal structure is a p-type thermoelectric material at high temperatures. Full article

Using the solid-state reactions method Na_0.55(Co,M)O₂ (M = Cr, Ni, Zn, W, and Bi) ceramics were prepared and their crystal structure, microstructure, electrophysical, thermophysical, and thermoelectric properties were studied. Doping of Na_0.55CoO₂ by transition or heavy metal oxides led to the increase in the grain size of ceramics, a decrease in electrical resistivity and thermal diffusivity values, and a sharp increase in the Seebeck coefficient, which resulted in essential enhancement of their thermoelectric properties. The largest power factor (1.04 mW/(m·K²) at 1073 K) and figure of merit (0.702 at 1073 K) among the studied samples possessed the Na_0.55Co_0.9Bi_0.1O₂ compound, which also demonstrated the highest values of the Seebeck coefficient (666 μV/K at 1073 K). The obtained results show that the doping of layered sodium cobaltite by different metal oxides allows for improving its stability, microstructure, and functional properties, which proves the effectiveness of the doping strategy for developing new thermoelectric oxides with enhanced thermoelectric performance. Full article

A comprehensive study of the thermoelectric properties of CuCr_0.99Ln_0.01S₂ (Ln = La…Lu) disulfides was carried out in a temperature range of 300 to 740 K. The temperature dependencies of the Seebeck coefficient, electrical resistivity, and thermal conductivity were analyzed. It was found that the cationic substitution of chromium with lanthanides in the crystal structure of layered copper–chromium disulfide, CuCrS₂ resulted in notable changes in the thermoelectric performance of CuCr_0.99Ln_0.01S₂. The cationic substitution led to an increase in the Seebeck coefficient and electrical resistivity and a thermal conductivity decrease. The highest values of the thermoelectric figure of merit and power factor corresponded to the praseodymium-doped sample and an initial CuCrS₂-matrix at 700–740 K. The cationic substitution with lanthanum, cerium, praseodymium, samarium, and terbium allowed for an enhancement of the thermoelectric performance of the initial matrix at a temperature range below 600 K. The cationic substitution of CuCrS₂ with lanthanum and praseodymium ions appeared to be the most promising approach for increasing the thermoelectric performance of the initial matrix. Full article

This research investigates the influence of synthesis kinetics on the structural and photocatalytic properties of chitosan–clay nanocomposites (Cs/MMT) and chitosan–hectorite nanocomposites (Cs/HET), employing an optimized initial stoichiometry of 1:3. Utilizing a variety of analytical techniques, including X-ray diffraction (XRD), transmission electron microscopy (TEM), and Fourier-transform infrared spectroscopy (FTIR), the study explores the structural evolution of the nanocomposites and their photocatalytic performance using semiconductor catalysts TiO₂ and ZnO. The findings emphasize the significant impact of reaction kinetics, particularly after 3 h of reaction time, on the structural features of the nanocomposites. Notably, Cs/MMT demonstrates greater crystalline stability compared to Cs/HET due to variations in octahedral cavity occupancy in the initial clays. FTIR and TEM analyses depict the progressive evolution of the nanocomposites during the reaction, shedding light on how reaction kinetics drive the formation of specific bonds within the nanocomposites. In terms of photocatalytic activity, this study provides insights into the complex dynamics of photocatalytic degradation, with a specific focus on the performance of TiO₂ and ZnO under diverse experimental conditions. The superior efficacy of TiO₂ as a catalyst, particularly when integrated with Cs/MMT nanocomposites, is unequivocally demonstrated, with degradation rates exceeding 80%. This preference stems from TiO₂ consistently exhibiting higher degradation rates compared to ZnO, attributed to structural disparities between montmorillonite and hectorite, influencing catalyst–support interactions. The findings underscore the critical importance of selecting suitable catalyst and support matrix combinations for optimizing performance in specific applications. Full article

Taking advantage of fact that the surface electrons of metallic nanoparticles (NPs) can be effectively released even at a low voltage bias, we demonstrate an improvement in the electrochemical performance of nanosized Prussian Blue (PB)-based secondary batteries through the incorporation of bare Ag or Ni NPs in the vicinity of the working PB NPs. It is found that the capacity for electrochemical energy storage of the 17 nm PB-based battery is significantly higher than the capacity of 10 nm PB-based, 35 nm PB-based or 46 nm PB-based batteries. There is a critical PB size for the highest electrochemical energy storage efficiency. The full specific capacity C_F of the 17 nm PB-based battery stabilized to 62 mAh/g after 130 charge–discharge cycles at a working current of I_W = 0.03 mA. The addition of 14 mass percent of Ag NPs in the vicinity of the PB NPs gave rise to a 32% increase in the stabilized C_F. A 42% increase in the stabilized C_F could be obtained with the addition of 14 mass percent of Ag NPs on the working electrode of the 35 nm PB-based battery. An enhancement in C_F was also found for electrodes incorporating bare Ni NPs but the effect was smaller. Full article

The charge properties and regularities of mutual influence of the electro-physical parameters in a metal (M)/insulator (I)/two-dimensional crystal heterostructure were studied. In one case, the transition metal dichalcogenide (TMD) MoS₂ was considered as a two-dimensional crystal, and in another the Weyl semi-metal (WSM) ZrTe₅, representative of a quasi-two-dimensional crystal was chosen for this purpose. By self-consistently solving the electrostatic equations of the heterostructures under consideration and the Fermi–Dirac distribution, the relationship between such parameters as the concentration of charge carriers, chemical potential, and quantum capacitance of the TMD (WSM), as well as the capacitance of the I layer and the interface capacitance I–TMD (WSM), and their dependence on the field electrode potential, have been derived. The conditions for the emergence of charge instability and the critical phenomena caused by it are also determined. Full article

In the quest to combat global warming, traditional thermal chemistry processes are giving way to selective photocatalysis, an eco-friendly approach that operates under milder conditions, using benign solvents like water. Benzaldehyde, a versatile compound with applications spanning agroindustry, pharmaceuticals, and cosmetics, serves as a fundamental building block for various fine chemicals. This study aims at enhancing benzaldehyde production sustainability by utilizing photooxidation of benzyl alcohol. Gold nanoparticle-based catalysts are renowned for their exceptional efficiency in oxidizing bio-based molecules. In this research, Au nanoparticles were anchored onto three distinct supports: $\mathrm{T}\mathrm{i}{\mathrm{O}}_2$, $\mathrm{Z}\mathrm{r}{\mathrm{O}}_2$, and graphitic carbon nitride (g-${\mathrm{C}}_3{\mathrm{N}}_4$). The objective was to investigate the influence of the support material on the selective photocatalysis of benzyl alcohol. In the preparation of g-${\mathrm{C}}_3{\mathrm{N}}_4$, three different precursors—melamine, urea, and a 50:50 mixture of both—were chosen to analyze their impact on catalyst performance. After 4 h of irradiation at 365 nm, operating under acidic conditions (pH = 2), the Au photocatalyst on graphitic carbon nitride support synthesized using urea precursor (Au@g-${\mathrm{C}}_3{\mathrm{N}}_{4\left(urea\right)}$) displayed the optimal balance between conversion (75%) and selectivity (85%). This formulation outperformed the benchmark Au@TiO₂, which achieved a similar conversion rate (80%) but exhibited lower selectivity (55%). Full article