Influence of high energy ball milling on structural,microstructural and optical properties of TiO2 nanoparticles

The influence of high-energy ball milling on structural, microstructural, and optical properties of TiO₂ by modifying the nanoparticle size was studied. Five samples were extracted at different milling times (0, 2, 4, 8, and 13 h). The average particle sizes estimated by dynamic light scattering (DLS) were 205, 155.8, 116.8, 82.9, and 82.7 nm at 0, 2, 4, 8, and 13 h, respectively. X-ray diffraction analysis confirmed progressive broadening of the peaks as the milling time elapsed. Besides, a correlation was found between d spacing and the average crystal size. The UV–Vis diffuse reflectance spectra of TiO₂ revealed a decrease in reflectance due to particle size reduction. Similarly, an alteration of the bandgap transition energy was presented, whose values gradually decreased from 2.966 eV to 2.861 eV for the sample without and with the maximum duration milling performed (13 h), respectively. Likewise, the SEM analysis showed a distribution in nanoparticle size that became more homogeneous and smaller average grain size as the milling duration was longer.     

The phosphorescence emission in undoped lead-halide Cs4PbBr6 single crystals at low temperature

Recently, all-inorganic cesium lead-halide perovskites have shown their promise for light emission applications, due to the excellent optical performance. Herein, we report that the initially nonphosphorescent undoped lead-halide Cs₄PbBr₆ single crystals (SCs) exhibit an ultralong phosphorescence emission under X-ray excitation at low temperatures. It is shown that the dramatic change has been taken place in radioluminescence spectra and the broad-band emission gradually appeared with the decrease of temperature. Below 210 K, the radioluminescence spectra can be deconvoluted into one narrow peak located at 530 nm and two broad peaks centered at 595 nm and 672 nm respectively. Subsequently, the time-dependent radioluminescence spectra in undoped lead-halide Cs₄PbBr₆ SCs were investigated. The ultralong phosphorescence emission can persist over 120 min at 70 K. We consider that ultralong phosphorescence originates from defect-related emission. To the best of our knowledge, our finding is the first time that undoped Cs₄PbBr₆ SCs exhibit the phosphorescence emission, which will offer a paradigm to motivate revolutionary applications on perovskite.     

Understanding δ-Bi2O3 fluorite degradation mechanism and related solutions for promising applications in distributed multigeneration

Oxygen selective membrane on the base of cermet δ-Bi₂O₃/Ag with an interpenetrating structure has the maximum potential efficiency of air separation. However, the degradation processes, including the phase degradation of fluorite δ-Bi₂O₃, do not make it possible to create a membrane with the required perfection and durability. In this work, the ordering of oxygen vacancies with the transformation of fluorite into the rhombohedral phase (S.G. R-3) was studied by powder HT XRD in situ at 600 °C on dense Bi_0.78Er_0.2Hf_0.02O_1.51 ceramics. Fast regeneration of disordered fluorite occurs at T = 640–700 °C. The phase degradation of fluorite due to the segregation of dopants at the second stage leads into stable phases - sillenite, tetragonal or rhombohedral phase (S.G. R-3m), depending on the composition of δ-Bi₂O₃. Fast regeneration of fluorite occurs when heated to 820 °C, which is unacceptable for membranes. Analysis of all available data allows us to propose approaches to optimize the composition of δ-Bi₂O₃ and technical solutions for creating durable oxygen selective membranes with promising use in distributed multigeneration. As a result of the analysis, a new solid electrolyte with better parameters was obtained.     

Defect control and ionic conductivity of oxynitride perovskite Sr0.83Li0.17Ta0.83O1.88N0.74

Perovskite lattice was tailored by introducing site vacancies and mixed anion composition, to produce Sr_0.83Li_0.17Ta_0.83O_1.88N_0.74 (Li02N). Further, Li02N was converted to a defect oxide Sr_0.83Li_0.17Ta_0.83O₃ (Li02O) by applying an optimized treatment: heating in air at 1173 K for 2 h. According to the neutron Rietveld refinement, Li02N and Li02O are tetragonal and orthorhombic, respectively, where the lattice volume of Li02O is significantly smaller than that of Li02N. The ionic conductivity (σ_ion) of Li02N and Li02O was evaluated by the ac impedance spectroscopy and the equivalent circuit analysis. Both Li02N (σ_ion = 10^?5.5 S/cm at 671 K) and Li02O (σ_ion = 10^?6.2 S/cm at 667 K) exhibited an Arrhenius behavior of ionic conductivity with activation energies of 0.87 eV and 0.75 eV, respectively. It is interpreted that the nitride component enhances the ionic conduction of Li02N, while the vacancy of the anion lattice makes an opposite effect.     

Influence of Se and Te substitutions at Tl-site of Tl(Ba,Sr)CaCu2O7 superconductor on the AC susceptibility and electrical properties

The Sr and Ba bearing Tl-1212 phase, Tl(Ba,Sr)CaCu₂O₇ is an interesting superconductor. The Sr only bearing TlSr₂CaCu₂O₇ is not easily prepared in the superconducting form. The Ba only bearing TlBa₂CaCu₂O₇ on the other hand does not show improvement in the transition temperature with elemental substitution. In this work the influence of multivalent Se (non-metal) and Te (metalloid) substitutions at the Tl-site of Tl_1-xM_x(Ba,Sr)CaCu₂O₇ (M = Se or Te) superconductors for x = 0–0.6 was studied. The samples were prepared via the conventional solid-state reaction method. XRD patterns showed a single Tl-1212 phase for x = 0 and 0.1 Se substituted samples. The critical current density at the peak temperature, T_p of the imaginary (χ”) part of the AC susceptibility (χ = χ’ +χ”), J_c-inter(T_p) for all samples was between 15 and 21 A cm⁻². The highest superconducting transition temperature was shown by the x = 0.3 Se-substituted sample (T_c-onset = 104 K, T_c-zero = 89 K, T_cχ’ = 104 K and T_p = 80 K). Te suppressed the superconductivity of Tl-1212 phase. The order of highest transition temperatures are as follows: Tl_1-xTe_x(Ba,Sr)CaCu₂O₇<Tl(Ba,Sr)CaCu₂O₇<Tl_1-xSe_x(Ba,Sr)CaCu₂O₇. This work showed that Se was better than Te in improving the transition temperature and flux pinning of the Tl-1212 phase. The roles of ionic radius of Se and Te on the superconductivity of Tl(Ba,Sr)CaCu₂O₇ are discussed in this paper.     

Human DDX17 Unwinds Rift Valley Fever Virus Non-Coding RNAs

Rift Valley fever virus (RVFV) is a mosquito-transmitted virus from the Bunyaviridae family that causes high rates of mortality and morbidity in humans and ruminant animals. Previous studies indicated that DEAD-box helicase 17 (DDX17) restricts RVFV replication by recognizing two primary non-coding RNAs in the S-segment of the genome: the intergenic region (IGR) and 5′ non-coding region (NCR). However, we lack molecular insights into the direct binding of DDX17 with RVFV non-coding RNAs and information on the unwinding of both non-coding RNAs by DDX17. Therefore, we performed an extensive biophysical analysis of the DDX17 helicase domain (DDX17_135–555) and RVFV non-coding RNAs, IGR and 5’ NCR. The homogeneity studies using analytical ultracentrifugation indicated that DDX17_135–555, IGR, and 5’ NCR are pure. Next, we performed small-angle X-ray scattering (SAXS) experiments, which suggested that DDX17 and both RNAs are homogenous as well. SAXS analysis also demonstrated that DDX17 is globular to an extent, whereas the RNAs adopt an extended conformation in solution. Subsequently, microscale thermophoresis (MST) experiments were performed to investigate the direct binding of DDX17 to the non-coding RNAs. The MST experiments demonstrated that DDX17 binds with the IGR and 5’ NCR with a dissociation constant of 5.77 ± 0.15 µM and 9.85 ± 0.11 µM, respectively. As DDX17_135–555 is an RNA helicase, we next determined if it could unwind IGR and NCR. We developed a helicase assay using MST and fluorescently-labeled oligos, which suggested DDX17_135–555 can unwind both RNAs. Overall, our study provides direct evidence of DDX17_135–555 interacting with and unwinding RVFV non-coding regions.     

Photoluminescence and energy transfer of Lu3Al5O12:Ce3+, Pr3+ phosphors

Ce³⁺ and Pr³⁺ co?doped Lu₃Al₅O₁₂ phosphors were synthesized by the sol–gel process, and their crystal structure, photoluminescence (PL) properties, and energy transfer (ET) from the Ce³⁺ to Pr³⁺ were studied. The Lu_2.94?yAl₅O₁₂:0.06Ce³⁺, yPr³⁺ phosphors (0.002 ≤ y ≤ 0.008) showed the green?yellow emission from the ²D_3/2 → ²F_{5/2, 7/2} transition of Ce³⁺ and the red emission at 610 and 637 nm, which were caused by the ¹D₂→³H₄ and ³P₀→³H₅ transitions of Pr³⁺, respectively. The optimal concentration of Pr³⁺ for efficient ET was found to be x = 0.006. The electric quadrupole?quadrupole interaction was responsible for the concentration quenching in the Lu_2.94?yAl₅O₁₂:0.06Ce³⁺, yPr³⁺ phosphors, based on Dexter's theory. The incorporation of Pr³⁺ for Lu³⁺ enhanced the red PL intensity in the Lu_2.94Al₅O₁₂:0.06Ce³⁺ phosphor.     

Preparation of transparent BaSO4 nanodispersions by high-gravity reactive precipitation combined with surface modification for transparent X-ray shielding nanocomposite films

BaSO₄ nanoparticles as important functional materials have attracted considerable research interests, due to their X-rays barrier and absorption properties. However, most of BaSO₄ nanoparticles prepared by traditional technology are nanopowders with broad size distribution and poor dispersibility, which may greatly limit their applications. To the best of our knowledge, the synthesis of transparent BaSO₄ nanodispersions was rarely reported. Here, we firstly present a novel and efficient method to prepare transparent and stable BaSO₄ nanodispersions with a relatively small particle size around 10 to 17 nm using a precipitation method in a rotating packed bed (RPB), followed by a modification treatment using stearic acid. Compared with the BaSO₄ prepared in a traditional stirred tank, the product prepared using an RPB has much smaller particle size and narrower size distribution. More importantly, by using RPB, the reaction time can be significantly decreased from 20 min to 18 s. Furthermore, the transparent BaSO₄-polyvinyl butyral nanocomposite films with good X-ray shielding performance can be easily fabricated. We believe that the stable BaSO₄ nanodispersions may have a wide range of applications for transparent composite materials and coatings with X-ray shielding performance for future research.     

Silver-substituted (Ag1-xCux)2ZnSnS4 solar cells from aprotic molecular inks

To battle the high open-circuit voltage deficit (V_OC,def) in kesterite (Cu₂ZnSnS₄ or CZTS) solar cells, a current field of research relates to point defect engineering by cation substitution. For example, by partly replacing Cu with an element of a larger ionic radius, such as Ag, the degree of Cu/Zn disorder decreases, and likewise does the associated band tailing. In this paper, solution-processed (Ag_1-xCu_x)₂ZnSnS₄ (ACZTS) samples are prepared through the aprotic molecular ink approach using DMSO as the solvent. The successful incorporation of silver into the CZTS lattice is demonstrated with relatively high silver concentrations, namely Ag/(Ag+Cu) ratios of 13% and 26%. The best device was made with 13% Ag/(Ag+Cu) and had an efficiency of 4.9%. The samples are compared to the pure CZTS sample in terms of microstructure, phase distribution, photoluminescence, and device performance. In the XRD patterns, a decrease in the lattice parameter c/a ratio is observed for ACZTS, as well as significant peak splitting with Ag addition for several of the characteristic kesterite XRD reflections. In addition to the improvement in efficiency, other advantageous effects of Ag-incorporation include enhanced grain growth and an increased band gap. A too high concentration of Ag leads to the formation of secondary phases such as SnS and Ag₂S as detected by XRD.     

Growth mechanism and gas-sensing characteristics of organic-additive-free zinc oxide of various shapes

Zinc oxide is widely used in gas sensors, solar cells, and photocatalysts because of its wide bandgap and exciton binding energy of 60 meV in various metal oxides. To use ZnO as a gas sensor, it is necessary to synthesize it with surface defects and a large specific surface area. In this study, hydrothermal synthesis without surfactants was employed to obtain organic-additive-free ZnO. For morphology control, we varied the ratio of the hydroxide ion concentration to the zinc ion concentration. To confirm the growth mechanism of ZnO, we performed X-ray diffraction, scanning electron microscopy, and transmission electron microscopy analyses. Raman spectroscopy and photoluminescence measurements were performed to analyze the surface properties. The Brunauer–Emmett–Teller method and probe stations were used to measure the specific surface area and sensitivity of the gas sensor, respectively. The results confirmed that flower-shaped ZnO is the most suitable gas-sensing material.