Preparation of CuIn1−xGaxS2 (x = 0.5) flowers consisting of nanoflakes via a solvothermal method

CuIn_1−xGa_xS₂ (x = 0.5) flowers consisting of nanoflakes were successfully prepared by a biomolecule-assisted solvothermal route at 220 °C for 10 h, employing copper chloride, gallium chloride, indium chloride and l-cysteine as precursors. The biomolecule l-cysteine acting as sulfur source was found to play a very important role in the formation of the final product. The diameter of the CuIn_0.5Ga_0.5S₂ flowers was 1-2 μm, and the thickness of the flakes was about 15 nm. The obtained products were characterized by X-ray diffraction (XRD), energy dispersion spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction spectroscopy (SAED), and UV-vis absorption spectroscopy. The influences of the reaction temperature, reaction time, sulfur source and the molar ratio of Cu-to-l-cysteine (reactants) on the formation of the target compound were investigated. The formation mechanism of the CuIn_0.5Ga_0.5S₂ flowers consisting of flakes was discussed.     

Direct synthesis and characterization of mesoporous Fe3O4 through pyrolysis of ferric nitrate-ethylene glycol gel

Mesoporous magnetite (Fe₃O₄) was successfully synthesized on a large scale by direct pyrolysis of ferric nitrate-EG (EG = ethylene glycol) gel in a one-end closed horizontal tube furnace in the air without using any template, additions, and carrier gas. The as-synthesized mesoporous Fe₃O₄ were characterized by powder X-ray diffraction (XRD), infrared spectra (IR), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), Brunauer-Emmett-Teller (BET), Barrett-Joyner-Halenda (BJH), and thermal gravimetric analysis (TGA). Results from TEM showed that the as-obtained Fe₃O₄ has mesoporous structure formed by the loose agglomeration of nanoparticles with diameter of about 6 nm, which was also confirmed by small-angle XRD and nitrogen adsorption analysis. Furthermore, vibrating sample magnetometer (VSM) measurements indicated that the saturated magnetization of the as-obtained mesoporous Fe₃O₄ was ferromagnetic with the saturation magnetization (Ms) and coercivity (Hc) of 46 emu/g and 136 Oe, respectively. In addition, a possible growth mechanism of mesoporous Fe₃O₄ was also discussed.     

Morphology and phase evolvement of Yb/Er co-doped NaYF4 microtubes prepared with YF3 submicrospindles as precursor

Hexagonal phase NaYF₄ microtubes co-doped with Yb³⁺ and Er³⁺ were synthesized through a hydrothermal process with YF₃ submicrospindles as precursor. The X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM) were utilized to characterize the structure and morphology of the as-prepared products. XRD results show that pure cubic NaYF₄ crystals can be obtained when reaction time is 2 h. While the product is mixture of cubic and hexagonal phase NaYF₄ when reaction time is from 7 to 20 h. Continuing to increase the reaction time to 24 h, the pure hexagonal NaYF₄ crystals were formed. The FE-SEM and TEM results show that the morphology of pure cubic NaYF₄ is spherical clusters composed of spherical nanoparticles with average diameter of about 100 nm and the pure hexagonal NaYF₄ crystals have tubular structure with out diameter of about 0.3-0.5 μm, inner diameter of about 0.5-1 μm and length ranging from 3 to 12 μm. The luminescence properties of Yb³⁺/Er³⁺ co-doped cubic and hexagonal phase NaYF₄ microcrystals were also studied. Under 980-nm excitation, the upconversion luminescence (UCL) intensity of hexagonal phase NaYF₄ microtubes is much stronger than that of cubic phase clusters. Moreover, both red and green upconversion are ascribed to the two-photon process. Therefore, hexagonal phase NaYF₄ microtubes with high UCL efficiency may have a potential application in photonic device.     

In situ synthesis of Co3O4/graphene nanocomposite material for lithium-ion batteries and supercapacitors with high capacity and supercapacitance

Co₃O₄/graphene nanocomposite material was prepared by an in situ solution-based method under reflux conditions. In this reaction progress, Co²⁺ salts were converted to Co₃O₄ nanoparticles which were simultaneously inserted into the graphene layers, upon the reduction of graphite oxide to graphene. The prepared material consists of uniform Co₃O₄ nanoparticles (15-25 nm), which are well dispersed on the surfaces of graphene nanosheets. This has been confirmed through observations by field emission scanning electron microscopy, transmission electron microscopy and atomic force microscopy. The prepared composite material exhibits an initial reversible lithium storage capacity of 722 mAh g⁻¹ in lithium-ion cells and a specific supercapacitance of 478 F g⁻¹ in 2 M KOH electrolyte for supercapacitors, which were higher than that of the previously reported pure graphene nanosheets and Co₃O₄ nanoparticles. Co₃O₄/graphene nanocomposite material demonstrated an excellent electrochemical performance as an anode material for reversible lithium storage in lithium ion cells and as an electrode material in supercapacitors.     

Synthesis of monodispersed ultrafine Bi2S3 nanocrystals

Monodispersed ultrafine Bi₂S₃ nanocrystals of ∼3 nm were synthesized via a facile and mild method, in which thioacetamide and bismuth oleate complex were used as the sulfur and bismuth precursors, respectively. The obtained Bi₂S₃ nanocrystals possessed a high surface area of 305 m² g⁻¹. The nanostructures of Bi₂S₃ nanocrystals were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and selective area electron diffraction (SAED) techniques. The optical property of the Bi₂S₃ nanocrystals was studied by photoluminescence spectroscopy. A remarkable blue shift and a band gap of ∼1.5 eV were observed. The shape of the Bi₂S₃ nanocrystals could be tuned by adjusting the initial Bi/S molar ratio and reaction temperature, respectively. A possible burst nucleation mechanism for this monodispersed ultrafine Bi₂S₃ nanocrystals was proposed.     

Morphology control and electrochemical properties of nanosize LiFePO4 cathode material synthesized by co-precipitation combined with in situ polymerization

Nanosize carbon coated LiFePO₄ cathode material was synthesized by in situ polymerization. The as-prepared LiFePO₄ cathode material was systematically characterized by X-ray diffraction, thermogravimetric-differential scanning calorimetry, X-ray photo-electron spectroscopy, field-emission scanning electron microscopy, and transmission electron microscopy techniques. Field-emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) images revealed that the morphology of the LiFePO₄ consists of primary particles (40-50 nm) and agglomerated secondary particles (100-110 nm). Each particle is evenly coated with an amorphous carbon layer, which has a thickness around 3-5 nm. The electrochemical properties were examined by cyclic voltammetry and charge-discharge testing. The as-prepared LiFePO₄ can deliver an initial discharge capacity of 145 mAh/g, 150 mAh/g, and 134 mAh/g at 0.2 C, 1 C, and 2 C rates, respectively, and exhibits excellent cycling stability. At a higher C-rate (5 C) a slight capacity loss could be found. However after being charge-discharge at lower C-rates, LiFePO₄ can be regenerated and deliver the discharge capacity of 145 mAh/g at 0.2 C.     

Mechanochemical synthesis of Al2O3-TiB2 nanocomposite powder from Al-TiO2-H3BO3 mixture

Alumina-titanium diboride nanocomposite (Al₂O₃-TiB₂) was produced using mixtures of titanium dioxide, acid boric and pure aluminum as raw materials via mechanochemical process. The phase transformation and structural characterization during mechanochemical process were utilized by X-ray diffractometry (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and thermogravimetric analyses (TG-DTA) techniques. A thermodynamic appraisal showed that the reaction between TiO₂, B₂O₃ and Al is highly exothermic and should be self-sustaining. XRD analyses exhibited that the Al₂O₃-TiB₂ nanocomposite was formed after 1.5 h milling time. The results indicate that increasing milling time up to 40 h had no significant effect other than refining the crystallite size.     

Effect of Mo/B atomic ratio on the microstructure and mechanical properties of Mo2FeB2 based cermets

Four series of Mo₂FeB₂ based cermets with the Mo/B atomic ratio in the range from 0.8 to 1.1 were prepared by reaction sintering process. The microstructure and crystalline phases were studied using scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDX) and X-ray diffractometry (XRD). The results indicate that the transverse rupture strength (TRS) of the cermets increases with an increase of Mo/B atomic ratio and shows a maximum value of 1.9 GPa at a Mo/B atomic ratio of 0.9. At a higher atomic ratio the TRS decreases. The hardness of the cermets decreases monotonically from 90.8 HRA to 88.8 HRA with an increase of Mo/B atomic ratio. In Mo-rich cermets with an atomic ratio of Mo/B above 1.0, a new M₂₃B₆ type phase (M₂₃B₆, where M represents a metal) is found. This phase has a lattice parameter a = 1.09 nm containing Mo, Fe, Cr and B with an atomic ratio close to 16:6:1:6 and is precipitated at the interface of Mo₂FeB₂ grains or at the Mo₂FeB₂ grain boundaries.     

An open aperture z-scan study of Sr2CeO4 blue phosphor

Sr₂CeO₄ blue phosphor has been prepared by the solid-state reaction method. The X-ray diffraction (XRD) study confirms the structure of the system to be orthorhombic. High resolution electron transmission microscopy reveals that Sr₂CeO₄ prepared by the solid state reaction method is composed of elongated spherical structures of length ∼0.2-0.6 μm and width ∼90-150 nm. The excitation spectrum shows a broad band which peaks at 275 nm. The emission spectrum shows a broad band which peaks at 467 nm when excited at 275 nm. The emission band is assigned to the energy transfer between the molecular orbital of the ligand and charge transfer (CT) state of the Ce⁴⁺ ion. The Commission International de l’Eclairage (CIE) co-ordinates are x = 0.15, and y = 0.23. The nonlinear absorption behavior of Sr₂CeO₄ has been investigated using the open aperture z-scan technique. The calculated effective two-photon absorption coefficient shows that the Sr₂CeO₄ blue phosphor is a promising optical limiting material.     

Solvothermal synthesis of monodisperse ultrasmall cubic-structure Ba2YbF7 nanocrystals with intense upconversion

A series of monodisperse ultrasmall Ba₂YbF₇ nanocrystals with intense upconversion emission were synthesized via a facile solvothermal method by using oleic acid as capping ligands. X-ray diffraction (XRD) and transmission electron microscopy (TEM) assays revealed that the as-synthesized Ba₂YbF₇ nanocrystals are of cubic structure, rather than the reported tetragonal structure. The cell parameter of the particles is 5.918 Å. The Er³⁺ or Tm³⁺ doped Ba₂YbF₇ nanocrystals with the size of sub-10 nm can give an intense upconversion emission under the 980 nm laser excitation and the upconversion processes were discussed. The Ba₂YbF₇ nanocrystals show a potential application as a bioimaging agent.     

Modification of TiO2 nanorods by Bi2MoO6 nanoparticles for high performance visible-light photocatalysis

In this work, TiO₂ nanorods were prepared by a hydrothermal process and then Bi₂MoO₆ nanoparticles were deposited onto the TiO₂ nanorods by a solvothermal process. The nanostructured Bi₂MoO₆/TiO₂ composites were extensively characterized by X-ray diffraction, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy and UV-vis diffuse reflectance spectroscopy. The photocatalytic activity of the Bi₂MoO₆/TiO₂ composites was evaluated by degradation of methylene blue. The Bi₂MoO₆/TiO₂ composites exhibit higher catalytic activity than pure Bi₂MoO₆ and TiO₂ for degradation of methylene blue under visible light irradiation (λ > 420 nm). Further investigation revealed that the ratio of Bi₂MoO₆ to TiO₂ in the composites greatly influenced their photocatalytic activity. The experimental results indicated that the composite with Bi₂MoO₆:TiO₂ = 1:3 exhibited the highest photocatalytic activity. The enhancement mechanism of the composite catalysts was also discussed.     

Synthesis of LiFePO4/C cathode materials through an ultrasonic-assisted rheological phase method

LiFePO₄/C active material was synthesized using an ultrasonic-assisted rheological phase method. In addition, polyvinyl butyral (PVB) was added in various concentrations to provide carbon coating on the surface of the LiFePO₄ particles for enhanced electrical conductivity. The crystal structure, morphology, and carbon coating layer of the synthesized LiFePO₄/C was analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), respectively. The electrochemical performance of LiFePO₄/C, such as initial capacity, rate capability, cycling performance and EIS, were also evaluated. The synthesized particle had a size range of 100-150 nm and a carbon layer of about 8 nm. The LiFePO₄/C (5 wt% PVB) delivered an initial discharge capacity of 167.5 mAh/g at a 0.1 C rate. It also showed an excellent capacity retention ratio of 100% after the 50th charging/discharging. EIS results demonstrate that the charge transfer resistance of the sample decreases greatly by coating with 5 wt% PVB.     

Mechanochemical synthesis of nanocrystalline ZnWO4 at room temperature

Single nanocrystalline ZnWO₄ powders were successfully synthesized by ball milling at room temperature. A stoichiometric mixture of ZnO and WO₃ in a 1:1 molar ratio was subjected to intense mechanical treatment in air using a planetary ball mill (Fritsch - Premium line - Pulversette No. 7) for a period varying from 5 to 300 min. The influence of the four different milling conditions was investigated on the formation of ZnWO₄. The products obtained were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Brunauer-Emmer-Teller (BET) surface area, infrared (IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The synthesis of ZnWO₄ powder started after 5 min milling time and finished after 30 min milling time at a higher speed (1000 rpm). The mechanical treatment up to 300 min did not lead to phase and structure change of ZnWO₄. The product obtained contained nanoparticles with a size of about 50 nm. The photocatalytic activity of the ZnWO₄ powders obtained was investigated by degradation of a model aqueous solution of Malachite Green (MG) upon UV-light irradiation.     

Hydrothermal synthesis of YBO3:Tb microflowers and their luminescence properties

Three-dimensional flowerlike YBO₃:Tb³⁺ phosphors have been successfully prepared by an efficient surfactant-free hydrothermal process directly without further sintering treatment. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray (EDS) spectrometry, selected area electron diffraction (SAED), photoluminescence (PL) spectra were used to characterize the samples. The as-obtained samples present flowerlike agglomerates composed of nanoflakes with thickness of 20 nm and high crystallinity in spite of the moderate reaction temperature of 180 °C. The reaction mechanism has been considered as a dissolution/precipitation mechanism; the self-assembly evolution process has been proposed on homocentric layer-by-layer growth style. The different luminescent intensity with different molar ratio of Y-Tb [Y:Tb = 8:2; 7:3; 6:4; 5:5; 4:6], YBO₃:Tb³⁺ phosphors exhibit different light (white, red, green) under ultraviolet excitation, which might find potential applications in the fields such as light display systems and optoelectronic devices.     

A facile method to prepare MoS2 with nanolameller-like morphology

MoS₂ nanolamellers were synthesized by a one-step oxidation-reduction reaction in solution, in which the (NH₄)₂MoS₄ and H₂C₂O₄·2H₂O were used as reactants and then calcined at 800 °C under N₂ for 1 h. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The diameter and nanoplate thickness of the obtained MoS₂ nanolamellers were approximately 80 nm and 20-30 nm, respectively. These novel structures of nanolamellers had potential applications in solid lubricants.     

Synthesis and phosphorescence properties of Mn, La and Ho in MgAl2Si2O8

Mn⁴⁺, La³⁺ and Ho³⁺ doped MgAl₂Si₂O₈-based phosphors were first synthesized by solid state reaction. They were characterized by thermogravimetry (TG), differential thermal analysis (DTA), X-ray powder diffraction (XRD), photoluminescence (PL) and scanning electron microscopy (SEM). The phosphors were obtained at about 1300 °C. They showed broad red and fuchsia-pink emission bands in the range of 610-715 nm and had a different maximum intensity when activated by UV illumination. Such a fuchsia-pink emission can be attributed to the intrinsic d-d transitions of Mn⁴⁺.     

Microstructure and properties of SiO2 matrix reinforced by BN nanotubes and nanoparticles

In order to overcome intrinsic brittleness and poor mechanical properties of SiO₂, two kinds of hexagonal boron nitride (h-BN) (boron nitride nanotubes (BNNTs) and boron nitride nanoparticles (BNNPs)) were employed to reinforce SiO₂ matrix. The mechanical properties, relative density and dielectric constant of the composites were investigated detailedly. Compared to the monolithic SiO₂, 5 wt% BNNTs/SiO₂ and 5 wt% BNNPs/SiO₂ composites exhibited excellent mechanical properties and low dielectric constant. Furthermore, phase composition and microstructure of the composites were analyzed thoroughly by X-ray diffraction, transmission electron microscopy, and field emission scanning electron microscopy.     

Effect of Mn content on the microstructure and mechanical properties of Mo2FeB2 based cermets

Five series of Mo₂FeB₂ based cermets with Mn addition between 0 and 10 wt% in 2.5 wt% increments were prepared by reaction sintering process. The effect of Mn content on the microstructure and crystalline phases was investigated by transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and X-ray diffraction (XRD). Hardness (HRA) and transverse rupture strength (TRS) were also measured. Mn addition improved the wettability of the Fe binder phase on the Mo₂FeB₂ hard phase, which resulted in a decrease in porosity and Mo₂FeB₂ grain size and an increase in phase uniformity. No Fe–Mn intermetallic compounds or other intermetallic compounds were detected with increasing Mn content. The TRS increased with increasing Mn content until it reached the maximum value at 10.0 wt% Mn addition. The hardness slightly increased with increasing Mn content firstly and then turned to decrease with increasing Mn content. The highest hardness was obtained for cermets with 5.0 wt% Mn addition.     

Synthesis, structure and optical properties of CoAl2O4 spinel nanocrystals

CoAl₂O₄ nanocrystals were synthesized by sol-gel method using citric acid as a chelating agent at low temperature. The as-synthesized samples were characterized by thermal analysis, X-ray powder diffraction, infrared spectroscopy and transmission electron microscopy. The results show that CoAl₂O₄ spinel is the only crystalline phase with a size of 10-30 nm in the temperature range 500-1000 °C. The temperature dependence of the distribution of Al³⁺ and Co²⁺ ions in the octahedral and tetrahedral sites in nanocrystals was investigated by X-ray photoelectron spectroscopy (XPS). It is observed that the inversion parameter decreases with increasing annealing temperature. Analysis of the absorption properties indicates that Co²⁺ ions are located in the tetrahedral sites as well as in the octahedral sites in the CoAl₂O₄ nanocrystals. The origin of the green color (300-500 nm absorption band) should be due to the octahedrally coordinated Co²⁺ ions.     

Synthesis and luminescence properties of Bi-doped YVO4 phosphors

YVO₄:Bi³⁺ phosphors have been prepared by a convenient high-temperature solid-state method. X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence (PL) technologies are used to study the luminescence properties of YVO₄:Bi³⁺ phosphors. The emission and excitation spectra of Bi³⁺ in the YVO₄ lattice have been investigated at room temperature. The excitation band peaks at 330 nm in a region among 250-400 nm, and the emission spectrum exhibits an intense yellowish-white broad emission centered at about 543 nm covering from 400 nm to 800 nm. The full width at half maximum (FWHM) is about 144 nm. The color coordinates of the as-synthesized YVO₄:Bi³⁺ phosphors are in a range of x = 0.358-0.374, y = 0.482-0.496. The dependence of the luminescence intensity on Bi³⁺ concentrations and heat treatment condition has also been discussed. In addition, we found that a little amount of flux NH₄Cl could enhance the Bi³⁺ luminescence intensity.