Search Results (22)

Nowadays, some amorphous and microcrystalline solid-state electrolytes (SSEs) with dual anions have attained high ionic conductivity and good compatibility with electrodes in all-solid-state lithium-ion batteries (ASSLIBs). In this work, crystalline SSEs of series A (Li_1+xTaO_1+xCl_4−x, −0.70 ≤ x ≤ 0.50) and B (LiTaO_2+yCl_2−2y, −1.22 ≤ y ≤ 0), having great application potential well over ambient temperatures, were prepared at 260–460 °C for 2–10 h using Li₂O, TaCl₅, and LiTaO₃ as the raw materials. The three-phase coexisting samples attained high σ values ranging from 5.20 to 7.35 mS cm⁻¹, which are among the reported high values of amorphous co-essential SSEs and other alloplasmatic crystalline ones. It is attributed to the synergistic effect of the polyanion trans-[O₂Cl₄] and cis-[O₄Cl₂] octahedra framework. Full article

Titanium metal is primarily produced via the Kroll process, which is characterized by a semi-continuous production flow and a lengthy process cycle, resulting in high production costs. Researchers have explored alternative methods for titanium production, including molten salt electrolysis, such as the Fray–Farthing–Chen (FFC), Ono Suzuki (OS), and University of Science and Technology Beijing (USTB) processes, aiming to achieve more economical production. Among these, the USTB process, a representative of soluble anode electrolysis, has shown significant promise. However, controlling oxygen concentration in titanium produced by soluble anode electrolysis remains a challenge. This study proposes a novel approach to enhance deoxidation efficiency in soluble anode electrolysis for titanium production by introducing yttrium chloride (YCl₃) into the molten salt electrolyte. Thermodynamic analysis and experimental validation demonstrate that the theoretical deoxidation limit for titanium can reach below 100 ppm under Y/YOCl/YCl₃ equilibrium. We report the successful synthesis of titanium powder with an oxygen concentration of 6000 ppm from titanium-carbon-oxygen solid solution. Under optimized conditions, the purity of the titanium powder reached 99.42%, demonstrating a new approach for producing high-purity titanium. This method, based on soluble anode electrolysis, offers a potential alternative to the conventional Kroll process. The research elucidates the fabrication process and analytical methods for titanium-carbon-oxygen solid solution, and employs a combination of analytical techniques, including XRD, SEM-EDS, and ONH Analyzer, for characterization of the electrolytic product, encompassing phase analysis, microstructure, and oxygen concentration testing. Full article

This structural study examines over 102 coordinate Cu(I) complexes with compositions such as C-Cu-Y (Y=HL, OL, NL, SL, SiL, BL, PL, Cl, Br, I, AlL, or SnL), N-Cu-Y (Y=OL, Cl), S-Cu-Y (Y=Cl, Br, I), P-Cu-Y (Y=Cl, I), and Se-Cu-Y (Y=Br, I). These complexes crystallize into three different crystal classes: monoclinic (seventy-two instances), triclinic (twenty-eight instances), and orthorhombic (eight instances). The Cu-L bond length increases with the covalent radius of the ligating atom. There are two possible geometries for coordination number two: linear and bent. A total of 21 varieties of inner coordination spheres exist, categorized into two hetero-types (C-Cu-Y, i.e., organometallic compounds and X-Cu-Y, i.e., coordination compounds). The structural parameters of hetero Cu(I) complexes were compared with trans-X-Cu (I)-X (homo) complexes and analyzed. The maximum deviations from linearity (180.0°) are, on average, 10.3° for Br-Cu(I)-Br, 16.6° for C-Cu(I)-Sn, and 35.5° for P-Cu(I)-I. These results indicate that ligand properties influence deviation from linearity, increasing in the order of hard < borderline < soft. Full article

[(Bn₂Cyclam)Y(N(SiMe₃)₂)] was prepared by reaction of H₂Bn₂Cyclam with Y[N(SiMe₃)₂]₃. The protonation of the macrocycle ligand in [(Bn₂Cyclam)Y(N(SiMe₃)₂)] is observed upon reaction with [HNMe₃][BPh₄] leading to the formation of [(HBn₂Cyclam)Y(N(SiMe₃)₂)][BPh₄]. DFT analysis of [(Bn₂Cyclam)Y(N(SiMe₃)₂)] showed that the HOMO is located on the anionic nitrogen atoms of the cyclam ring indicating that protonation follows orbital control. Addition of H₂Bn₂Cyclam and H₂(^3,5-tBu2Bn)₂Cyclam to a 1:3 mixture of YCl₃ and LiCH₂SiMe₃ in THF resulted in the formation of [((C₆H₄CH₂)BnCyclam)Y(THF)(µ-Cl)Li(THF)₂] and [Y{(η³-^3,5-tBu2Bn)₂Cyclam}Li(THF)], respectively. The reaction of H₂^3,5-tBu2Bn₂Cyclam with Y(CH₂SiMe₃)₃(THF)₂ was studied and monitored by a temperature variation NMR experiment revealing the formation of [(^3,5-tBu2Bn₂Cyclam)Y(CH₂SiMe₃)]. Preliminary catalytic assays have shown that [Y{(η³-^3,5-tBu2Bn)₂Cyclam}Li(THF)] is a very efficient catalyst for the intramolecular hydroamination of 2,2-diphenyl-pent-4-enylamine. Full article

Cesium lead iodide (CsPbI₃) perovskite nanocrystals (NCs) are a promising material for red-light-emitting diodes (LEDs) due to their excellent color purity and high luminous efficiency. However, small-sized CsPbI₃ colloidal NCs, such as nanocubes, used in LEDs suffer from confinement effects, negatively impacting their photoluminescence quantum yield (PLQY) and overall efficiency. Here, we introduced YCl₃ into the CsPbI₃ perovskite, which formed anisotropic, one-dimensional (1D) nanorods. This was achieved by taking advantage of the difference in bond energies among iodide and chloride ions, which caused YCl₃ to promote the anisotropic growth of CsPbI₃ NCs. The addition of YCl₃ significantly improved the PLQY by passivating nonradiative recombination rates. The resulting YCl₃-substituted CsPbI₃ nanorods were applied to the emissive layer in LEDs, and we achieved an external quantum efficiency of ~3.16%, which is 1.86-fold higher than the pristine CsPbI₃ NCs (1.69%) based LED. Notably, the ratio of horizontal transition dipole moments (TDMs) in the anisotropic YCl₃:CsPbI₃ nanorods was found to be 75%, which is higher than the isotropically-oriented TDMs in CsPbI₃ nanocrystals (67%). This increased the TDM ratio and led to higher light outcoupling efficiency in nanorod-based LEDs. Overall, the results suggest that YCl₃-substituted CsPbI₃ nanorods could be promising for achieving high-performance perovskite LEDs. Full article

A number of alkali organometallic complexes with suitable thermodynamic properties and high capacity for hydrogen storage have been synthesized; however, few transition metal–organic complexes have been reported for hydrogen storage. Moreover, the synthetic processes of these transition metal–organic complexes via metathesis were not well characterized previously, leading to a lack of understanding of the metathesis reaction. In the present study, yttrium phenoxide and lanthanum phenoxide were synthesized via metathesis of sodium phenoxide with YCl₃ and LaCl₃, respectively. Quasi in situ NMR, UV-vis, and theoretical calculations were employed to characterize the synthetic processes and the final products. It is revealed that the electron densities of phenoxides in rare-earth phenoxides are lower than in sodium phenoxide due to the stronger Lewis acidity of Y³⁺ and La³⁺. The synthetic process may follow a pathway of stepwise formation of dichloride, monochloride, and chloride-free species. Significant decreases in K-band and R-band absorption were observed in UV-vis, which may be due to the weakened conjugation effect between O and the aromatic ring after rare-earth metal substitution. Two molecular structures, i.e., planar and nonplanar, are identified by theoretical calculations for each rare-earth phenoxide. Since these two structures have very close single-point energies, they may coexist in the materials. Full article

The production of lactic acid and value-added chemicals (such as hydroxypropanone, glycolic acid, and formic acid) directly from Ulva prolifera via one-step catalytic process was studied. The effect of different amounts of YCl₃-derived catalysts on the hydrothermal conversion of carbohydrates in Ulva prolifera was explored, and the reaction conditions were optimized. In this catalytic system, rhamnose could be extracted from Ulva prolifera and converted in situ into lactic acid and hydroxypropanone at 160 °C, while all the glucose, xylose, and rhamnose were fractionated and completely converted to lactic acid at 220 °C or at a higher temperature, via several consecutive and/or parallel catalytic processes. The highest yield of lactic acid obtained was 31.4 wt% under the optimized conditions. The hydrothermal conversion of Ulva prolifera occurred rapidly (within 10 min) and showed promise to valorize Ulva prolifera. Full article

Liquid–liquid phase separation (LLPS) underlies the formation of membrane-free organelles in eukaryotic cells and plays an important role in the development of some diseases. The phase boundary of metastable liquid–liquid phase separation as well as the cloud point temperature of some globular proteins characterize the phase behavior of proteins and have been widely studied theoretically and experimentally. In the present study, we used a regression and classification neural network to deal with the phase behavior of lysozyme and bovine serum albumin (BSA). We predicted the cloud point temperature and solubility of a lysozyme solution containing sodium chloride by regression and the reentrant phase behavior of BSA in YCl₃ solution containing a surfactant dodecyl dimethyl amine oxide (DDAO) by classification. Specifically, our network model is capable of predicting (a) the solubility of lysozyme in the range: pH 4.0–5.4, temperature 0–25 °C, and NaCl concentration 2–7% (w/v); (b) the cloud point temperature of lysozyme in the range: pH 4.0–4.8, NaCl concentration 2–7%, and lysozyme concentration 0–400 mg/mL; and (c) the phase behavior of BSA in the range: DDAO 1–60 mM, BSA 30–100 mg/mL, and YCl₃ 1–20 mM. We experimentally tested the model at some prediction points with a high accuracy, which means that deep neural networks can be applicable in qualitative and quantitive analysis of liquid–liquid phase separation. Full article

Due to the increasing demand for rare earth elements (REE) resources in the market and the shortage of their direct sources, the research on REE in coal fly ash (CFA) has attracted the increasing attention of scholars because of its high content of rare earth. To extract and separate REE from the leaching solution of CFA, the method of solvent extraction after acid leaching is usually adopted. In this paper, the leaching solution of coal fly ash from Panbei, south China, with an average REE content of 478 μg/g, was taken as the research object. The extracted di-2-Ethylhexyl phosphonic acid (P204) was used to explore the solvent extraction effect and mechanism. When performed with the conditions: pH value of 2.1, oil-water ratio (O/A) of 1, extraction time of 25 min, solvent concentration of 6% and temperature of 30 ℃, the extraction rates of La, Ce, Pr, Nd, and Y were 89.16%, 94.11%, 95.56%, 96.33%, and 99.80%, respectively. It was indicated that the P204 extraction system separated REE well from the aqueous phase. The structure of the extraction complex was deduced by taking yttrium as an object of analysis, and the extraction mechanism equation was determined by using the slope method. In this extraction system, the molecular formula of the complex is YCl₂(HA₂) and the enthalpy change (△H) is +86.68 kJ/mol, which provides theoretical guidance for the extraction of REE in industrial production. Full article

In this study, a CO₂ carbonization method is introduced for the preparation of 1D yttrium oxide powders. Using YCl₃ as the raw material, sodium hydroxide was initially used to completely precipitate Y³⁺ into yttrium hydroxide, and then CO₂ was introduced into the yttrium hydroxide slurry for homogenization-like carbonization to obtain yttrium carbonate precipitation. Then, by studying the effects of carbonization conditions, such as the temperature, CO₂ flow rate, and stirring speed, on the morphology and phases of yttrium carbonate, the temperature was observed to exert a greater effect than the other experimental parameters on the morphology and structure of the carbonized products. Finally, Y₂(CO₃)₃·2H₂O nanoneedles were obtained at optimal conditions. The carbonized crystals of the acicular yttrium carbonate precipitate because of the solution supersaturation and then quickly complete their crystal growth process through the oriented attachment (OA) and Ostwald ripening (OR) mechanisms. After heat treatment, yttrium carbonate retained a good crystal morphology and produced Y₂O₃ nanoneedles with a length of 1–2 μm and a width of 20–30 nm. Full article

YBa₂Cu₃O_7−δ (YBCO) thin films with the addition of Cl were prepared on Hastelloy tape by the extremely low fluorine metal-organic deposition (MOD) technique. The composition and microstructure of the present samples were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). It was revealed that the Cl-added YBCO thin films achieved better texture and density compared with the pure YBCO films. The superconducting properties at magnetic fields were measured using the magnetic property measurement system (MPMS). The results showed that the sample onset transition temperature (T_{c, on}) did not change significantly after the addition of Cl. The critical current density (J_c) in the presence of YBCO with the addition of Cl increased significantly. Meanwhile, both the J_c and gravitational force (F_p) of the (Cl, Hf) co-added YBCO films were further enhanced at different magnetic fields. The thermodynamic analysis of the BaCO₃ removal reaction revealed that the addition of Cl to YBCO formed chlorine compounds, which were effective in avoiding the formation of BaCO₃. Further, the calculation results of the Gibbs free energy at different pressure quotients showed that the stability of the relevant chlorine compounds occurred in the order of BaCl₂ > CuCl₂ > YCl₃ and the oxidation of BaCl₂ to BaO required a higher temperature compared to BaF₂, implying the potential advantages of inhibiting the a-axis growth. Full article

Scintillation detection has attracted great interest in nuclear medicine, nuclear radiation detection, high-energy physics, and non-destructive inspection. The elpasolite crystals with Ce³⁺ dopants are promising for these endeavors due to their modest light yield and extremely good proportionality when excited by the gamma ray. Moreover, the ⁶Li and ³⁵Cl isotopes in elpasolite crystals endow them with excellent neutron detection capability. These features allow not only a high energy resolution but also a high detection sensitivity. The elpasolite scintillators also enable the precisely dual detection of gamma/neutron signals through pulse height discrimination (PHD) or pulse shape discrimination (PSD). In this work, we review recent investigations on using the typical elpasolite scintillators, including Ce³⁺-doped Cs₂LiYCl₆ (CLYC), Cs₂LiLaCl₆ (CLLC), and Cs₂LiLaBr₆ (CLLB), for the monitoring of gamma rays and neutrons. The scintillation properties, detection mechanism, and elpasolite crystal structure are also discussed with the aim of improving high-energy ray detection ability. Full article

Cs₂LiYCl₆: Ce³⁺ (CLYC) is a dual-mode gamma-neutron scintillator with a medium gamma-ray resolution and pulse-shape discrimination (PSD) capability. The PSD performance of CLYC is greatly weakened when coupled with silicon photomultipliers (SiPMs) because of SiPMs’ low detection efficiency for the ultrafast Core-Valence-Luminescence (CVL) component under gamma excitation. In our previous work, the PSD Figure-of-Merit (FoM) value was optimized to 2.45 at the gamma-equivalent energy region of the thermal neutron by using the charge comparison method. However, this value was reduced to 1.37 at the lower gamma-equivalent energy region of more than 325 keV, and neutrons were difficult to distinguish from gamma rays. Hence, new algorithms should be studied to improve the PSD performance at low gamma-equivalent energy regions. Convolutional Neural Networks (CNNs) have excellent image recognition capabilities, and thus, neutron and gamma-ray waveforms can be discriminated by their characteristics through a known training set. In this study, neutron and gamma-ray waveforms were measured with a ¹³⁷Cs source and moderated ²⁵²Cf source via an SiPM array-coupled CLYC detector and divided into two groups: training and PSD testing. The CNN training set comprised ¹³⁷Cs characteristic gamma-ray waveforms and thermal neutron waveforms that were discriminated by the charge comparison method from the training group. A CNN with two convolution-pooling layers was designed to accomplish PSD with the test group. The PSD FoM value of the CNN method was calculated to be 37.20 at the gamma-equivalent energy region of more than 325 keV. This result was much higher than that of the charge comparison method, indicating that neutrons and gamma rays could be better distinguished with the CNN method, especially at low gamma-equivalent energy regions. Full article

The solubility in triple water-salt systems containing NdCl₃, PrCl₃, YCl₃, TbCl₃ chlorides, and water-soluble fullerenol C₆₀(OH)₂₄ at 25 °C was studied by isothermal saturation in ampoules. The analysis for the content of rare earth elements was carried out by atomic absorption spectroscopy, for the content of fullerenol—by electronic spectrophotometry. The solubility diagrams in all four ternary systems are simple eutonic, both consisting of two branches, corresponding to the crystallization of fullerenol crystal-hydrate and rare earth chloride crystal-hydrates, and containing one nonvariant point corresponding to the saturation of both solid phases. On the long branches of C₆₀(OH)₂₄*18H₂O crystallization, a C₆₀(OH)₂₄ decreases by more than 2 orders of magnitude compared to the solubility of fullerenol in pure water (salting-out effect). On very short branches of crystallization of NdCl₃*6H₂O, PrCl₃*7H₂O, YCl₃*6H₂O, and TbCl₃*6H₂O, the salting-in effect is clearly observed, and the solubility of all four chlorides increases markedly. The four diagrams cannot be correctly approximated by the simple one-term Sechenov equation (SE-1), and very accurately approximated by the three-term modified Sechenov equation (SEM-3). Both equations for the calculation of nonelectrolyte solubility in electrolyte solutions (SE-1 and SEM-3 models) are obtained, using Pitzer model of virial decomposition of excess Gibbs energy of electrolyte solution. It is shown that semi-empirical equations of SE-1 and SEM-3 models may be extended to the systems with crystallization of crystal-solvates. Full article

Tools for remote radiation sensing are essential for environmental safety and nuclear power applications. The use of unmanned aerial systems (UASs) equipped with sensors allows for substantially reducing the radiation exposure of personnel. An ambient temperature Cs₂LiYCl₆:Ce³⁺ (CLYC) elpasolite scintillation sensor for simultaneous gamma and neutron measurements was designed as a user-friendly “plug and fly” module integrated into an octocopter robotic platform. Robot Operating System (ROS) was used to analyze the sensor’s data. The measured CLYC’s energy resolution was <5% at 662 keV gamma rays; neutron flux was measured using ⁶Li(n,α)t reaction. Time and GPS data were combined with radiation data in the ROS, supporting real time monitoring and assessment tasks, as well as radiation source search missions. Because UASs can be irradiated, radiation damage of the sensor and robot’s electronics was estimated using FLUKA code. Full article