Effect of Temperature and Pressure on Structural and Optical Properties of Organic-Inorganic Hybrid Manganese Halides.

Organic-inorganic hybrid metal halides have recently attracted attention in the global research field for their bright light emission, tunable photoluminescence wavelength, and convenient synthesis method. This study reports the detailed properties of (C10H16N)2MnBr4, which emits bright green light with a high photoluminescence quantum yield. Results of powder X-ray diffraction, photoluminescence, thermogravimetric analysis, and Raman spectra show the phase transition of (C10H16N)2MnBr4 at 430 K. This phase transition was identified as the solid to liquid state of (C10H16N)2MnBr4. Moreover, the pressure- and temperature-induced relationship between structural and optical properties in (C10H16N)2MnBr4 can be identified. This investigation provides deep insights into the luminescent properties of metal halide crystals and promotes further research.

Chromium Ion Pair Luminescence: A Strategy in Broadband Near-Infrared Light-Emitting Diode Design.

Portable near-infrared (NIR) light sources are in high demand for applications in spectroscopy, night vision, bioimaging, and many others. Typical phosphor designs feature isolated Cr3+ ion centers, and it is challenging to design broadband NIR phosphors based on Cr3+-Cr3+ pairs. Here, we explore the solid-solution series SrAl11.88-xGaxO19:0.12Cr3+ (x = 0, 2, 4, 6, 8, 10, and 12) as phosphors featuring Cr3+-Cr3+ pairs and evaluate structure-property relations within the series. We establish the incorporation of Ga within the magentoplumbite-type structure at five distinct crystallographic sites and evaluate the effect of this incorporation on the Cr3+-Cr3+ ion pair proximity. Electron paramagnetic measurements reveal the presence of both isolated Cr3+ and Cr3+-Cr3+ pairs, resulting in NIR luminescence at approximately 650-1050 nm. Unexpectedly, the origin of broadband NIR luminescence with a peak within the range 740-820 nm is related to the Cr3+-Cr3+ ion pair. We demonstrate the application of the SrAl5.88Ga6O19:0.12Cr3+ phosphor, which possesses an internal quantum efficiency of ∼85%, a radiant flux of ∼95 mW, and zero thermal quenching up to 500 K. This work provides a further understanding of spectral shifts in phosphor solid solutions and in particular the application of the magentoplumbites as promising next-generation NIR phosphor host systems.

The Simple Method of Preparation of Highly Carboxylated Bacterial Cellulose with Ni- and Mg-Ferrite-Based Versatile Magnetic Carrier for Enzyme Immobilization.

The bacterial cellulose (BC) is a versatile biopolymer of microbial origin characterized by high purity and unusual water and material properties. However, the native BC contains a low number of functional groups, which significantly limits its further application. The main goal of its effective modification is to use methods that allow the unusual properties of BC to be retained and the desired functional group to be efficiently introduced. In the present study, the new magnetic carrier based on functionalized citric acid (CA) bacterial cellulose was developed and tested to support critical industrial enzymes such as lipase B from Candida antarctica and phospholipase A from Aspergillus oryzae. The applied method allowed BC to be effectively modified by citric acid and a sufficient number of carboxylic groups to be introduced, up to 3.6 mmol of COOH per gram of dry mass of the prepared carrier. The DSC and TGA analyses revealed carrier stability at operational temperatures in the range of 20 °C to 100 °C and substantially influenced the amount of the introduced carboxyl groups on carrier properties. Both enzymes' immobilization significantly improves their thermal stability at 60 °C without a significant thermal and pH optima effect. The analyzed enzymes showed good operational stability with a significant residual activity after ten cycles of repeated uses. The new magnetic carrier based on highly carboxylated bacterial cellulose has a high application capability as matrix for immobilization the various enzymes of industrial interest.

Chromium(III)-Doped Fluoride Phosphors with Broadband Infrared Emission for Light-Emitting Diodes.

Two types of infrared fluoride phosphors, Cr3+-doped K3AlF6 and K3GaF6, were developed in this research. The K3Al1-xF6:xCr3+ and K3Ga1-yF6:yCr3+ fluoride phosphors were proven to be pure phase via X-ray diffraction refinement, which demonstrated that the procedure can be applied to large-scale production. Electron paramagnetic resonance measurements indicated that Cr3+ ions in cubic with respect to noncubic are coupled better with K3GaF6 than with K3AlF6. The main differences between these two phosphors, the site symmetry and pressure behavior of the spectra, were obtained in temperature- and pressure-dependent spectra. According to the calculation results, Cr3+ in fluorine coordination at ambient pressure indicates an intermediate crystal field. For the phosphor-converted light-emitting diodes (LEDs) fabricated from these two phosphors, the spectral range is from 650 to 1000 nm, which resulted in a radiant flux of 7-8 mW with an input power of 1.05 W. The research reveals detailed luminous properties, which will lead to a new way of studying Cr3+-doped fluoride phosphors and their application in LEDs.

Multi-Site Cation Control of Ultra-Broadband Near-Infrared Phosphors for Application in Light-Emitting Diodes.

Near-infrared (NIR) phosphors are fascinating materials that have numerous applications in diverse fields. In this study, a series of La3Ga5GeO14:Cr3+ phosphors, which was incorporated with Sn4+, Ba2+, and Sc3+, was successfully synthesized using solid-state reaction to explore every cationic site comprehensively. The crystal structures were well resolved by combining synchrotron X-ray diffraction and neutron powder diffraction through joint Rietveld refinements. The trapping of free electrons induced by charge unbalances and lattice vacancies changes the magnetic properties, which was well explained by a Dyson curve in electron paramagnetic resonance. Temperature and pressure-dependent photoluminescence spectra reveal various luminescent properties between strong and weak fields in different dopant centers. The phosphor-converted NIR light-emitting diode (pc-NIR LED) package demonstrates a superior broadband emission that covers the near-infrared (NIR) region of 650-1050 nm. This study can provide researchers with new insight into the control mechanism of multiple-cation-site phosphors and reveal a potential phosphor candidate for practical NIR LED application.

A Long Cycle-Life High-Voltage Spinel Lithium-Ion Battery Electrode Achieved by Site-Selective Doping.

Spinel LiNi0.5 Mn1.5 O4 (LNMO) is a promising cathode candidate for the next-generation high energy-density lithium-ion batteries (LIBs). Unfortunately, the application of LNMO is hindered by its poor cycle stability. Now, site-selectively doped LNMO electrode is prepared with exceptional durability. In this work, Mg is selectively doped onto both tetrahedral (8a) and octahedral (16c) sites in the Fd 3 ‾ m structure. This site-selective doping not only suppresses unfavorable two-phase reactions and stabilizes the LNMO structure against structural deformation, but also mitigates the dissolution of Mn during cycling. Mg-doped LNMOs exhibit extraordinarily stable electrochemical performance in both half-cells and prototype full-batteries with novel TiNb2 O7 counter-electrodes. This work pioneers an atomic-doping engineering strategy for electrode materials that could be extended to other energy materials to create high-performance devices.

Control of Luminescence by Tuning of Crystal Symmetry and Local Structure in Mn4+ -Activated Narrow Band Fluoride Phosphors.

Mn4+ -doped fluoride phosphors have been widely used in wide-gamut backlighting devices because of their extremely narrow emission band. Solid solutions of Na2 (Six Ge1-x )F6 :Mn4+ and Na2 (Gey Ti1-y )F6 :Mn4+ were successfully synthesized to elucidate the behavior of the zero-phonon line (ZPL) in different structures. The ratio between ZPL and the highest emission intensity υ6 phonon sideband exhibits a strong relationship with luminescent decay rate. First-principles calculations are conducted to model the variation in the structural and electronic properties of the prepared solid solutions as a function of the composition. To compensate for the limitations of the Rietveld refinement, electron paramagnetic resonance and high-resolution steady-state emission spectra are used to confirm the diverse local environment for Mn4+ in the structure. Finally, the spectral luminous efficacy of radiation (LER) is used to reveal the important role of ZPL in practical applications.

Sulphated TiO2 Reduced by Ammonia and Hydrogen as an Excellent Photocatalyst for Bacteria Inactivation.

This study presents a relatively low-cost method for modifying TiO2-based materials for photocatalytic bacterial inactivation. The photocatalytic inactivation of Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus epidermidis) bacteria using modified sulphated TiO2 was studied. The modification focused on the reduction of TiO2 by ammonia agents and hydrogen at 400-450 °C. The results showed a high impact of sulphate species on the inactivation of E. coli. The presence of these species generated acid sites on TiO2, which shifted the pH of the reacted titania slurry solution to lower values, around 4.6. At such a low pH, TiO2 was positively charged. The ammonia solution caused the removal of sulphate species from TiO2. On the other hand, hydrogen and ammonia molecules accelerated the removal of sulphur species from TiO2, as did heating it to 450 °C. Total inactivation of E. coli was obtained within 30 min of simulated solar light irradiation on TiO2 heat-treated at 400 °C in an atmosphere of Ar or NH3. The S. epidermidis strain was more resistant to photocatalytic oxidation. The contact of these bacteria with the active titania surface is important, but a higher oxidation force is necessary to destroy their cell membrane walls because of their thicker cell wall than E. coli. Therefore, the ability of a photocatalyst to produce ROS (reactive oxidative species) will determine its ability to inactivate S. epidermidis. An additional advantage of the studies presented is the inactivation of bacteria after a relatively short irradiation time (30 min), which does not often happen with photocatalysts not modified with noble metals. The modification methods presented represent a robust and inexpensive alternative to photocatalytic inactivation of bacteria.

Applying the FMR Technique to Analyzing the Influence of Nitriding on the Magnetic Properties of Steel.

This paper presents the relationship between the chemical composition and size of steel balls, the parameters of the nitriding process, and their magnetic properties, defined in this study by ferromagnetic resonance (FMR) and SQUID. Balls made from AISI 1010 and AISI 52100 steels, with diameters of 2.5 and 3 mm, respectively, were investigated. On samples made of AISI 1010 and AISI 52100 steel, single-phase layers of iron nitrides γ' with a thickness of gmp = 50 and 37 µm, respectively, were produced. Then, the samples were annealed at a temperature of 520 °C for 4 h in an inert atmosphere (N2/Ar) at a pressure of 200 Pa. After the nitriding processes, steel balls were subjected to standard physical metallurgy and X-ray examinations. During annealing of nitrided layers with a two-phase layer of iron nitrides, at first, the transformation of the ε phase into the γ' phase with the release of nitrogen into the atmosphere takes place. The FMR signals did not originate from isolated ions, but from more magnetically complex systems, e.g., Fe-Fe pairs or iron clusters, while the observed FMR line position is normally even lower and occurs for a magnetic induction below 200 mT. The fact that the magnetic centers did not contain mainly isolated Fe ions, additionally confirmed the abnormal increase in resonance signal intensity as a function of temperature, which is a behavior inconsistent with the Curie-Weiss law. The results obtained from measurements by the SQUID method, recording variations in magnetization as a function of temperature, confirm the untypical reinforcement of the magnetic conditions of the samples with the increase in temperature. For the samples tested, the magnetization was relatively weaker when the tests were conducted in a stronger magnetic field.

Defect Mediated Improvements in the Photoelectrochemical Activity of MoS2/SnS2 Ultrathin Sheets on Si Photocathode for Hydrogen Evolution.

Solar-driven water electrolysis to produce hydrogen is one of the clean energy options for the current energy-related challenges. Si as a photocathode exhibits a large overpotential due to the slow hydrogen evolution reaction (HER) kinetics and hence needs to be modified with a cocatalyst layer. MoS2 is a poor HER cocatalyst due to its inert basal plane. Activation of the MoS2 basal plane will facilitate HER kinetics. In this study, we have incorporated SnS2 into MoS2 ultrathin sheets to induce defect formation and phase transformation. MoS2/SnS2 composite ultrathin sheets with a Sn2+ state create a large number of S vacancies on the basal sites. The optimized defect-rich MoS2/SnS2 ultrathin sheets decorated on surface-modified Si micro pyramids as photocathodes show a current density of -23.8 mA/cm2 at 0 V with an onset potential of 0.23 V under acidic conditions, which is higher than that of the pristine MoS2. The incorporation of SnS2 into 2H-MoS2 ultrathin sheets not only induces a phase but also can alter the local atomic arrangement, which in turn is verified by their magnetic response. The diamagnetic SnS2 phase causes a decrease in symmetry and an increase in magnetic anisotropy of the Mo3+ ions.

Enhancement of self-trapped excitons and near-infrared emission in Bi3+/Er3+ co-doped Cs2Ag0.4Na0.6InCl6 double perovskite.

Erbium (Er) complexes are used as optical gain materials for signal generation in the telecom C-band at 1540 nm, but they need a sensitizer to enhance absorption. Na+ substitution for Ag+ and Bi3+ doping at the In3+ site is a possible strategy to enhance the broadband emission of Cs2AgInCl6, which could be used as a sensitizer for energy transfer to rare-earth elements. Herein, self-trapped exciton (STE) energy transfer to Er3+ at 1540 nm in double perovskite is reported. An acid precipitation method was used to synthesize Cs2AgInCl6 and its derivatives with Er3+, Bi3+, and Na+. Bare Cs2AgInCl6:Er emission signals were found to be weak at 1540 nm, but Bi3+ doping increased them by 12 times, and Bi3+ and Na+ doping increased signal intensity by up to 25 times. Electron paramagnetic resonance spectroscopy characterized a decrease in axial symmetry over the Er3+ ions after the substitutions of Na+ and Bi3+ in Cs2AgInCl6 at low temperatures (<7 K) for the first time. Moreover, an increase in pressure compressed the structure, which tuned the STE transition for free exciton emission, and a further increase in pressure distorted the cubic phase above 70 kbar.

Crystallographic-Site-Specific Structural Engineering Enables Extraordinary Electrochemical Performance of High-Voltage LiNi0.5 Mn1.5 O4 Spinel Cathodes for Lithium-Ion Batteries.

The development of reliable and safe high-energy-density lithium-ion batteries is hindered by the structural instability of cathode materials during cycling, arising as a result of detrimental phase transformations occurring at high operating voltages alongside the loss of active materials induced by transition metal dissolution. Originating from the fundamental structure/function relation of battery materials, the authors purposefully perform crystallographic-site-specific structural engineering on electrode material structure, using the high-voltage LiNi0.5 Mn1.5 O4 (LNMO) cathode as a representative, which directly addresses the root source of structural instability of the Fd 3 ¯ m structure. By employing Sb as a dopant to modify the specific issue-involved 16c and 16d sites simultaneously, the authors successfully transform the detrimental two-phase reaction occurring at high-voltage into a preferential solid-solution reaction and significantly suppress the loss of Mn from the LNMO structure. The modified LNMO material delivers an impressive 99% of its theoretical specific capacity at 1 C, and maintains 87.6% and 72.4% of initial capacity after 1500 and 3000 cycles, respectively. The issue-tracing site-specific structural tailoring demonstrated for this material will facilitate the rapid development of high-energy-density materials for lithium-ion batteries.

Optical study of Yb(3+)/Yb(2+) conversion in CaF(2) crystals.

Yb(3+) ions with various site symmetries have been observed in the absorption and emission spectra of Yb(3+):CaF(2) crystals, both γ-irradiated and annealed in hydrogen. The absorption intensity value is found to be much higher for the γ-irradiated crystal and strongly dependent on the gamma dose. The UV absorption spectra of γ-irradiated and H(2)-annealed CaF(2):5 at.% Yb(3+) crystals are quite similar. Yb(2+) absorption bands are observed at 360, 315, 271, 260, 227 and 214 nm, which are called A, B, C, D, F and G bands, respectively. For γ-irradiated CaF(2):30 at.% Yb(3+), an additional band at 234 nm can be seen. It is suggested that only a negligible amount of Yb(3+) ions are converted into Yb(2+) under the γ-irradiation. The presence of Yb(2+) is confirmed by the 565 and 540 nm luminescence under 357 nm excitation. It is also suggested that the excitation in the A, C, D and F absorption bands of Yb(2+) gives rise to photo-ionization of Yb(2+) ions and electrons in the conduction band to form the excited Yb(3+) ions which emit IR Yb(3+) luminescence.The UV absorption and emission spectra obtained for γ-irradiated and H(2)-annealed crystals have different structures. This suggests that different mechanisms are responsible for the creation of Yb(2+) ions. γ-irradiation favours Yb(2+) isolated centres by reduction of Yb(3+) ions located at Ca(2+) lattice sites, whereas annealing in hydrogen favours Yb(2+) centres neighbouring Yb(3+) ions when a Yb(3+) ion pair captures a Compton electron. Also, γ-irradiation does not change the position of Yb(3+) ions converted into Yb(2+) in the CaF(2) lattice. In the case of H(2) annealing, a Yb(3+) ion converted to Yb(2+) is shifted to the Ca(2+) position in the lattice.