MoO2@MoS2 Nanoarchitectures for High‐Loading Advanced Lithium‐Ion Battery Anodes

The capacity loading per unit area is of importance as specific capacity while evaluating the lithium‐ion battery anode. However, the low conductivity of several advanced anode materials (such as molybdenum sulfide, MoS₂) prohibits the wide application of materials. Nanostructural engineering becomes a key to overcome the obstacles. A one‐step in situ conversion reaction is employed to synthesize molybdenum oxide (MoO₂)–MoS₂ core–shell nanoarchitectures (MoO₂@MoS₂) by partially sulfiding MoO₂ into MoS₂ using sulfur. The MoO₂@MoS₂ displays a 3D architecture constructed by hundreds of MoS₂ ultrathin sheets with several layers arranged and fixed to an MoO₂ particle vertically with the size in the range of 200–500 nm. MoO₂ acts as the molybdenum source for the synthesis of MoS₂, as well as the conductive substrate. The designed 3D architectures with empty space between MoS₂ layers can prevent the damage originated from volume change of MoS₂ undergoing charge/discharge process. The lithium storage capacities of the MoO₂@MoS₂ 3D architectures are higher and the stability has been significantly improved compared to pure MoS₂. 4 mAh cm^?2 capacity loading of MoO₂@MoS₂ has been achieved with a specific capacity of more than 1000 mAh g^?1.     

Tunable Upconversion Emissions from Lanthanide-doped Monodisperse β-NaYF4 Nanoparticles

We report upconversion multicolor tuning based on uniform β-NaYF₄:Yb/Tm/Er nanoparticles. The as-synthesized nanoparticles with an average diameter of 25 nm are well dispersed in a wide range of nonpolar solvents including hexane, cyclohexane, dichloromethane, and toluene. These nanoparticles show intense upconversion emissions and the color output can be precisely modulated by adjusting activator ratios of Tm³⁺ to Er³⁺. Dopant-concentration dependent emission properties of the triply doped particle system are also investigated. In addition, we demonstrate that these nanoparticles can be readily transferred to polar solvents such as ethanol and water by growing a thin silica layer (10 nm) around the particles, providing potential applications in biological labeling and imaging.     

Control Synthesis of Air‐Stable Morphology Tunable Pb‐Free Cs2SnI6 Perovskite Nanoparticles and Their Photodetection Properties

Pb‐free Cs₂SnI₆ perovskite nanoparticles with different morphologies are synthesized using hot injection process and precise control of ligand chemistry. Size dependent band gap variation is studied to evaluate quantum‐confinement effect in the system. Stable and fast photodetector with high current gain is fabricated by using the nanoparticles as colloidal ink.     

<Superscript>87</Superscript>Rb NMR study of the magnetic structure of the quasi-two-dimensional antiferromagnet RbFe(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> on a triangular lattice

⁸⁷Rb nuclear magnetic resonance was experimentally studied in a quasi-two-dimensional Heisenberg antiferromagnet RbFe(MoO₄)₂. Dipole fields at the ⁸⁷Rb nuclei were found over a wide range of temperatures and static magnetic fields. Magnetic structures in the ordered phase were determined at various magnetic fields.     

Iron Precursor Decomposition in the Magnesium Combustion Flame: A New Approach for the Synthesis of Particulate Metal Oxide Nanocomposites

Powders of Fe–Mg–O nanocomposite particles have been grown using a novel chemical vapor synthesis approach that employs the decomposition of a metalorganic precursor inside the metal combustion flame. After annealing in controlled gas atmospheres composition distribution functions, structure and phase stability of the obtained magnesiowüstite nanoparticles are measured with a combination of techniques such as inductively coupled plasma‐optical emission spectroscopy, energy dispersive X‐ray spectroscopy, X‐ray diffraction, and scanning and transmission electron microscopy. Complementary Mössbauer spectroscopy measurements reveal that depending on Fe loading and temperature of annealing either metastable and superparamagnetic solid solutions of Fe³⁺ ions in periclase (MgO) or phase separated mixtures of MgO and ferrimagnetic magnesioferrite (MgFe₂O₄) nanoparticles can be obtained. The described combustion technique represents a novel concept for the production of mixed metal oxide nanoparticles. Adressing the impact of selected annealing protocols, this study underlines the great potential of vapor phase grown non‐equilibrium solids, where thermal processing provides means to trigger phase separation and, concomitantly, the emergence of new magnetic properties.     

The properties of transparent conducting molybdenum-doped ZnO films grown by radio frequency magnetron sputtering

Transparent conducting molybdenum-doped zinc oxide films are prepared by radio frequency(RF) magnetron sputtering at ambient temperature.The MoO3 content in the target varies from 0 to 5 wt%,and each film is polycrystalline with a hexagonal structure and a preferred orientation along the c axis.The resistivity first decreases and then increases with the increase in MoO3 content.The lowest resistivity achieved is 9.2 × 10-4.cm,with a high Hall mobility of 30 cm2.V-1.s-1 and a carrier concentration of 2.3×1020 cm-3 at an MoO3 content of 2 wt%.The average transmittance in the visible range is reduced from 91% to 80% with the increase in the MoO3 content in the target.     

Temperature‐induced phase transformations in Na2WO4 and Na2MoO4 crystals

Temperature‐dependent Raman studies on Na₂WO₄and Na₂MoO₄ crystals were performed in order to obtain information on structural changes induced by temperature evolution. The stability of the cubic phase of Na₂WO₄and Na₂MoO₄crystals was assessed and our results indicate that this phase is stable in the 8–823 K and 15–773 K ranges for Na₂WO₄ and Na₂MoO₄, respectively. The crystal of Na₂WO₄ shows a phase transition occurring at 833 K. Na₂MoO₄undergoes a sequence of three phase transitions, which were observed at 783–803, 823–913 and 943–950 K. In both crystals, a strong first‐order phase transition occurs as indicated by the behavior of the Raman modes: the Raman bands split and new bands appear below 100 cm⁻¹. These transitions are connected with tilting and/or rotations of the WO₄and MoO₄ tetrahedra, which leads to a disorder at the WO₄and MoO₄ sites. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis of MoO2 particles during oxidation of bulk molybdenum samples by supercritical water

It was found that bulk samples of molybdenum 〈Mo〉 are oxidized by supercritical water forming nanoparticles of monocline MoO₂. The average size of nanoparticles obtained at uniform heating of 〈Mo〉 with supercritical water was about 27 nm, and the size of agglomerates of nanoparticles was ≤ 1 μm. From time dependence of the amount of formed H₂ n _H2(t), we have determined kinetic parameters of 〈Mo〉 transition to MoO₂ particles. The dependence dn _H2/dt is characterized by the presence of two pronounced maxima. This is explained by the change of mutual diffusion of H₂ and H₂O molecules along with the growth of thickness of the layer of MoO₂ nanoparticles.     

Amplification of Solar Energy Conversion in Quantum‐Confined CdSe‐Sensitized TiO2 Photonic Crystals by Trapping Light

Photonic effects amplifying solar energy conversion are reported in titania inverse opals sensitized with quantum‐confined CdSe films. TiO₂ inverse opals (i‐TiO₂‐o) and unstructured nanocrystalline TiO₂ (nc‐TiO₂) films are sensitized with CdSe deposited via successive ionic layer adsorption and reaction (SILAR) by generating Se^2? in situ under inert atmosphere, and the film absorbance is tuned by the number of SILAR cycles. Photonic effects are investigated while varying the i‐TiO₂‐o stop band position relative to CdSe films’ absorbance. i‐TiO₂‐o films with stop band at 700 and 560 nm are sensitized with CdSe having absorption edges at 600 and 650 nm thus tuning absorbance to the red and the blue of the stop band. Significant amplification in photon‐to‐current conversion efficiency is measured when CdSe films prepared via two cycles are adsorbed on i‐TiO₂‐o with a stop band at 700 nm, with a maximum average enhancement factor equal to 6.7 ± 1.6 at 640 nm, 60 nm to the blue of the stop band center, relative to nc‐TiO₂ sensitized with comparable CdSe amounts. The gain is observed over a wide frequency range to the blue of the stop band and is greatest when film absorbance was low. The photocurrent gain is not a result of differences in the rates of charge separation or charge transport, and occurs in the same frequency range where absorbance amplification is measured to the blue of the 700‐i‐TiO₂‐o stop band, and is thus attributed to slow light effects enhancing absorbance in the photonic crystal environment.     

Ionic conductivity of double sodium-scandium and cesium-zirconium molybdates

The electrical properties of the Na₃Sc(MoO₄)₃ and Cs₂Zr(MoO₄)₃ compounds are investigated using impedance spectroscopy (1–10⁶ Hz) in the temperature range 100–650°C. Double molybdates in the form of a fine-crystalline powder are obtained by solid-phase synthesis in air at 450–600°C for 20–50 h. It is found that the temperature dependence of the ionic conductivity of ceramic samples exhibits anomalies at temperatures of 605 ± 5°C for Na₃Sc(MoO₄)₃ and 425 ± 15°C for Cs₂Zr(MoO₄)₃ due to the phase transitions, which are confirmed by the data of thermal analysis. Above the superionic transitions, the ionic conductivity reaches 0.084 S/cm (650°C) for Na₃Sc(MoO₄)₃ and 0.002 S/cm (462°C) for Cs₂Zr(MoO₄)₃.     

In situ pressure-induced solid-state amorphization in Sm2(MoO4)3, Eu2(MoO4)3 and Gd2(MoO4)3 crystals: chemical decomposition scenario

The effect of pressure on the phase transformations in Sm₂(MoO₄)₃, Gd₂(MoO₄)₃ and Eu₂(MoO₄)₃ crystals has been studied in situ using synchrotron radiation. All three isostructural compounds undergo a structural phase transition at 2.2-2.8 GPa to a new phase, which is interpreted as a possible precursor of amorphization. Amorphization in these crystals occurs irreversibly over a wide pressure range, and its mechanism, interpreted as a chemical decomposition, is found to be weakly affected by the degree of hydrostaticity.     

Electroluminescence enhancement in ultraviolet organic light‐emitting diode with graded hole‐injection and ‐transporting structure

Electroluminescent intensity and external quantum efficiency (EQE) in ultraviolet organic light‐emitting diodes (UV OLEDs) have been remarkably enhanced by using a graded hole‐injection and ‐transporting (HIT) structure of MoO₃/N,N ′‐bis(naphthalen‐1‐yl)‐N,N ′‐bis(phenyl)‐benzidine/MoO₃/4,4′‐bis(carbazol‐9‐yl)biphenyl (CBP). The graded‐HIT based UV OLED shows superior short‐wavelength emis‐ sion with spectral peak of ～410 nm, maximum electroluminescent intensity of 2.2 mW/cm² at 215 mA/cm² and an EQE of 0.72% at 5.5 mA/cm². Impedance spectroscopy is employed to clarify the enhanced hole‐injection and ‐transporting capacity of the graded‐HIT structure. Our results provide a simple and effective approach for constructing efficient UV OLEDs. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Optical properties and ultrafast electron dynamics in gold–silver alloy and core–shell nanoparticles

Silver and gold are the two most popular metals used for many nanoparticle applications, such as surface enhanced Raman scattering or surface enhanced fluorescence, in which the local field enhancement associated with the excitation of the localized surface-plasmon–polariton resonance (SPR) is exploited. Therefore, tunability of the SPR over a wide energy range is required. For this purpose we have investigated core–shell nanoparticles composed of gold and silver with different shell thicknesses as well as the impact of alloying on these nanoparticles due to a tempering process. The nanoparticles were prepared by subsequent deposition of Au and Ag atoms or vice versa on quartz substrates followed by diffusion and nucleation. Their linear extinction spectra were measured as a function of shell thickness and annealing temperature. It turned out that different gold shell thicknesses on silver cores allow a tuning of the SPR position from 2.79 to 2.05 eV, but interestingly without a significant change on the extinction amplitude. Heating of core–shell nanoparticles up to only 540 K leads to the formation of alloy nanoparticles, accompanied by a back shift of the SPR to 2.60 eV. Calculations performed in quasi-static approximation describe the experimental results quite well and prove the structural assignments of the samples. In additional experiments, we applied the well-established persistent spectral hole burning technique to the alloy nanoparticles in order to determine the ultrafast dephasing time T ₂. We obtained a dephasing time of T ₂=(8.1±1.6) fs, in good agreement with the dephasing time of T _2,∞=8.9 fs, which is already included in the dielectric function of the bulk.     

Preparation of phosphors AEu(MoO4)2 (A?=?Li, Na, K and Ag) by?sol-gel method

A series of double molybdates phosphors AEu(MoO₄)₂ (A = Li, Na, K and Ag) have been prepared by sol-gel method. Their crystal structure and luminescent properties have also been investigated in a comparable way. The crystallization processes of the phosphor precursors were characterized by X-ray diffraction (XRD) and thermogravimetry-differential thermal analysis (TG-DTA). Field emission scanning electron microscopy (FE-SEM) was also used to characterize the shape and size distribution of the phosphors. Samples except KEu(MoO₄)₂ showed tetragonal scheelite structure in the range of our experiments, and no phase transition appeared. Phosphor KEu(MoO₄)₂ possessed two structures, and the phase transition took place at about 800°C. All samples with high purity could be obtained at about 500°C for 5 hours, and they all showed intense red light peaked at 616 nm originated from ⁵D₀→⁷F₂ emission of Eu³⁺ under the excitation of 465 nm or 394 nm light. The excitation spectra of phosphors AEu(MoO₄)₂ (A = Li, Na, and K) are composed of a strong broad charge transfer (CT) band and some sharp lines, and the relative intensity of CT band, the two strongest absorption lines at 395 nm and 465 nm are comparative, so these three phosphors are good red phosphor candidates for violet or blue LEDs. For the excitation spectrum of phosphor AgEu(MoO₄)₂, intensities of CT band and the absorption line at 395 nm are much weaker than that of line at 465 nm, thus phosphor AgEu(MoO₄)₂ is only suit for GaN-based blue LED.     

Highly efficient solid-state synthesis of carbon-encapsulated ultrafine MoO<Subscript>2</Subscript> nanocrystals as high rate lithium-ion battery anode

A simple and highly efficient method is developed for the one-step in situ preparation of carbon-encapsulated MoO₂ nanocrystals (MoO₂@C) with core-shell structure for high-performance lithium-ion battery anode. The synthesis is depending on the solid-state reaction of cyclopentadienylmolybdenum tricarbonyl dimer with ammonium persulfate in an autoclave at 200 °C for 30 min. The large amount of heat generated during the explosive reaction cleaves the cyclopentadiene ligands into small carbon fragments, which form carbon shell after oxidative dehydrogenation coating on the MoO₂ nanocrystals, resulting in the formation of core-shell structure. The MoO₂ nanocrystals have an equiaxial morphology with an ultrafine diameter of 2–8 nm, and the median size is 4.9 nm. Hundreds of MoO₂ nanocrystals are encapsulated together by the worm-like carbon shell, which is amorphous and about 3–5 nm in thickness. The content of MoO₂ nanocrystals in the nanocomposite is about 69.3 wt.%. The MoO₂@C anode shows stable cyclability and retains a high reversible capacity of 443 mAh g^?1 after 50 cycles at a current density of 3 A g^?1, owing to the effective protection of carbon shell.     

Vibrations and chemical states of iron ions in soda‐lime glasses determined by element‐specific X‐ray analyses

We systematically study medium‐range structures including more than three neighboring atoms around iron ions (Fe²⁺ and Fe³⁺) in soda‐lime glass samples with low iron oxide concentrations (M_Fe2O3) and a wide number ratio of Fe²⁺ to all iron ions (Fe²⁺/Σ_nFe). The precise medium‐range structures around iron ions in glass have not yet been revealed because of a lack of the appropriate measurement methods. To avoid this problem, we used element‐specific nuclear resonant inelastic scattering (NRIS) with synchrotron X‐rays to observe the vibrations of iron ions (⁵⁷Fe). The vibrations are related to medium‐range structures with more than three neighboring atoms and to the potential asymmetry and the coordination environment, around iron ions. The NRIS method has high sensitivity and can measure over a wide concentration range. Linear combination fitting of the X‐ray absorption fine structure spectra, which measures only the first neighbors but is a faster than using the NRIS method, was also used additionally. A systematically produced set of glasses with 0.015–5 wt% M_Fe2O3 and 0–0.85 Fe²⁺/Σ_nFe was measured with these methods. It was found that the soda‐lime glass possessed two different medium‐range structures with different iron ion valences (~2+ or ~3+), which were determined by the Fe²⁺/Σ_nFe, and that these structures were generated during production of the glass. Moreover, these medium‐range structures were the same from 0.015 to 5 wt% M_Fe2O3.     

Room‐Temperature Synthesis of High Surface Area Anatase TiO2 Exhibiting a Complete Lithium Insertion Solid Solution

The synthesis of highly divided anatase TiO₂ nanoparticles displaying 300 m² g^?1 surface area is achieved by following a two‐step synthetic process at room temperature. The particles exhibit a needle‐like morphology composed of self‐assembled 4 nm nanoparticles. The crystallization process from amorphous TiO₂.1.6H₂O to oriented aggregation of anatase TiO₂ proceeds according to a slow solid dehydration process taking place in a large range of pH in deionized water (1 < pH < 12) or alternatively when including a low amount of NH₄F_(aq) in solution. Driven by their high surface area enhancing the chemical/electrochemical reactivity, it is reported in the case of the anatase TiO₂ that a modification in the lithium insertion mechanism is no longer attributable to a two‐phase reaction between the two‐end members Li_εTiO₂ and Li_0.5±αTiO₂ when downsizing the particle size, but instead through a complete solid solution all along the composition range.     

High‐pressure polarized Raman spectra of Gd2(MoO4)3: phase transitions and amorphization

Polarized Raman spectra of a single crystal of gadolinium molybdate [Gd₂(MoO₄)₃] were obtained between 1 atm and 7 GPa. Using a mixture of alcohols as the pressure‐transmitting medium, YY, ZZ, XY components of scattering matrices were measured. The ZZ spectra were also obtained in argon. Five phase transitions and amorphization were identified. The first and second transitions are reversible, while amorphization is not. In alcohol, amorphization is observed above 6.5 GPa. With argon as the pressure‐transmitting medium, amorphization is progressive and begins above 3 GPa. The spectral changes with pressure affect the high wavenumber bands attributed to symmetric and antisymmetric MoO₄ stretching modes as well as the very low wavenumber modes such as librations of the tetrahedra. This means that both short‐range and long‐range organizations of the tetrahedra are involved in these phase transitions. The amorphization mechanism and its dependence on the pressure‐transmitting medium are discussed, and the steric hindrance between polyhedra is believed to be the most relevant mechanism. The TO and LO low wavenumber modes of A₁ symmetry, observed in the Y(ZZ)Y and Z(YY)Z geometries, respectively, below 50 cm⁻¹, soften continuously through the first three phases when increasing pressure. The strong A₂ mode observed in the Z(XY)Z spectra exhibits the same anomalous behavior by decreasing from 53 to 46 cm⁻¹ at 2 GPa. The softening of these modes is related to the orientation change of tetrahedra observed by ab initio calculations when the volume of the cell is decreased. These orientation changes can explain the wavenumber decrease of the Mo O stretching modes above 2 GPa, which indicates an increase of Mo coordination. Copyright © 2010 John Wiley & Sons, Ltd.     

A potential red phosphor LiGd(MoO4)2:Eu for light-emitting diode application

Eu³⁺-doped LiGd(MoO₄)₂ red phosphor was synthesized by solid-state reaction, and its photoluminescent properties were measured. The effect of Eu³⁺ doping concentration on PL intensity was investigated, and the optimum concentration of Eu³⁺ doped in LiGd(MoO₄)₂ was found to be 30 mol%. Compared with Y₂O₂S:0.05Eu³⁺, Na_0.5Gd_0.5MoO₄:Eu³⁺ and KGd(MoO₄)₂:Eu³⁺, the LiGd(MoO₄)₂:Eu³⁺ phosphor showed a stronger excitation band around 395 nm and a higher intensity red emission of Eu³⁺ under 395 nm light excitation. For the first time, intensive red light-emitting diodes (LEDs) were fabricated by combining phosphor and a 395 nm InGaN chip, confirming that the LiGd(MoO₄)₂:Eu³⁺ phosphor is a good candidate for LED applications.