Controlled synthesis and photoluminescence properties of BaXO4 (X = W, Mo) hierarchical nanostructures via a facile solution route

Shape-controlled synthesis of BaWO₄ hierarchical nanostructures has been achieved in a mixed solvent of water and ethanol at room temperature. By simply adjusting the volume ratio of C₂H₅OH and H₂O (R ratio), the size and shape of BaWO₄ nanostructures, such as shuttle-like and ellipsoid-like, are successfully controlled. This simple method has been extended to synthesize BaMoO₄ hierarchical nanostructures. Both BaWO₄ and BaMoO₄ hierarchical nanostructures exhibited new green emission peaks at 558 and 560 nm, respectively.     

Facile synthesis of BaMoO4 and BaMoO4/BaWO4 heterostructures with type -I band arrangement and enhanced photoluminescence properties

A series of BaMoO₄ and BaMoO₄/BaWO₄ phosphors were successfully prepared via a polyacrylamide gel method and low temperature calcination technology. The effects of sintering temperature and mass percentage of BaMoO₄/BaWO₄ on the phase purity, functional group, surface morphology, charge state, photoluminescence properties and photocatalytic activity of the prepared products were studied in detail. The results indicate that the BaMoO₄ phosphor is a scheelite tetragonal structure with high crystallinity. The photoluminescence spectra indicates that the phosphors have a strong blue emission peak at 440 nm with excitation wavelength of 282 nm for the BaMoO₄ phosphor, and three emission peaks at 400, 440 and 460 nm with excitation wavelength of 284 nm for the BaMoO₄/BaWO₄ phosphors. These photoluminescence behaviors can be ascribed to the ¹T₂→¹A₁ transition, Jahn–Teller distorted tetrahedral symmetry of [MoO₄]^2- and surface defect. Photocatalytic experiments further confirmed that the BaMoO₄/BaWO₄ phosphors exhibit a high recombination rate of electron hole pairs. The result further indicates that the type-I band arrangement structure of BaMoO₄/BaWO₄ phosphors is beneficial to enhance the photoluminescent properties of single-phase phosphors. This study provides a novel route for preparing the type-I band arrangement structure composite phosphors with high photoluminescent properties and potential applications in light emitting devices, optoelectronic devices, laser devices and white pigments.     

Self-assembled 3D flower-like NaY(MoO4)2:Eu microarchitectures: Hydrothermal synthesis, formation mechanism and luminescence properties

Self-assembled 3D flower-like NaY(MoO₄)₂:Eu³⁺ microarchitectures were successfully synthesized by a glycine-assisted hydrothermal method at 180 °C. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM) were employed to characterize the as-obtained products. It was found that morphology modulation could be easily realized by changing the time of hydrothermal reaction system. 3D flower-like NaY(MoO₄)₂:Eu³⁺ microarchitectures were formed with 72 h reaction time. The formation mechanism for flower-like architecture was proposed on the basis of a series of time-dependent experiments. The NaY(MoO₄)₂:Eu³⁺ powders obtained can be effectively excited by 396 nm light, and exhibit strong red emission around 615 nm, attributed to the Eu³⁺⁵D₀ → ⁷F₂ transition. An investigation on the photoluminescence (PL) properties of NaY(MoO₄)₂:Eu³⁺ obtained revealed that the luminescence properties were correlated with the morphology and size.     

A simple route to synthesis of BaCO3 nanostructures in water/ethylene glycol mixed solvents

Barium carbonate (BaCO₃) nanostructures with different morphologies were synthesized using Ba(NO₃)₂ and (NH₄)₂CO₃ in the water/ethylene glycol (EG) mixed solvents by oil bath heating at 80 °C for 30 min. The molar ratio of water to EG had an effect on the morphology of BaCO₃. The products were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM).     

A facile chemical route to α-Zn3(PO4)2·4H2O hierarchical sphere structures assembled by nanosheets

Novel α-Zn₃(PO₄)₂·4H₂O hierarchical sphere structures have been synthesized by a simple chemical method through the reaction between zinc acetate and orthophosphoric acid by using cetyltrimethylammonium bromide (CTAB) as capping reagent at room temperature. The structures and morphologies of the as-obtained products were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscopy (TEM). The influences of the synthetic parameters on the morphologies of the final products were investigated. The experimental results clearly show that both the concentration of CTAB aqueous solution and the concentration of initial reagents play important roles in the formation of the α-Zn₃(PO₄)₂·4H₂O hierarchical sphere structure. Detailed proofs indicated that the process of crystal growth was dominated by a self-assembly growth mechanism.     

Luminescent properties of BaWO4 films prepared by cell electrochemical technique

Highly crystallized BaWO₄ films (45 × 30 mm²) have been prepared by cell electrochemical technique at room temperature. X-ray diffraction measurement reveals that the as-prepared BaWO₄ thin films have a scheelite structure. Under cell conditions, due to the decrease of crystal size and disappearance of large clusters, films' homogeneity has been improved markedly. With the UV excitation the peculiar and tunable luminescence of BaWO₄ films has been observed. Investigations uncover that exciting energies can be transferred among different emission centers, and that the yellow emission is probably relevant to the vacancies of Ba in the outermost layers of films.     

Hydrothermal synthesis,characterization, and luminescence of BaWO4 nanorods

Barium tungstate (BaWO₄) nanorods were synthesized by a hydrothermal process with the assistant of cetyltrimethyl ammonium bromide (CTAB). The samples were analyzed by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), and photoluminescence measurements. The XRD and FT-IR results show that BaWO₄ samples can be indexed as a pure tetragonal scheelite structure. The SEM results show that the morphologies are nanorods with a diameter about 45 nm and a length exceeding 1 μm. The CTAB and “oriented attachment” play key roles in the growth of BaWO₄ nanorods in the hydrothermal process. When excited at 265 nm, BaWO₄ nanorods show the intrinsic emission band centered at 467 nm. The calculated luminescence lifetime of WO₄ ^2? in BaWO₄ is 8.9 μs.     

Synthesis and characterization of novel flower-like CeF3 nanostructures via a rapid microwave method

Novel flower-like CeF₃ nanostructures with a mean diameter of 190 nm were successfully synthesized via a rapid and facile microwave irradiation route using ethylenediaminetetraacetic acid disodium as the complexing reagent. The products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and photoluminescence (PL). XRD patterns showed that the CeF₃ nanoflowers were hexagonal phase and had good crystallinity and purity. TEM and SEM images showed that the as-prepared CeF₃ samples displayed 3D flower-like nanostructures and had uniform sizes and morphologies. The experimental results revealed that the as-prepared CeF₃ nanoflowers might be assembled by nanodisks. The formation process of the CeF₃ nanoflowers was preliminarily investigated.     

Facile synthesis of MnV2O6 nanostructures with controlled morphologies

MnV₂O₆ nanostructures including nanorods, nanobelts, and nanosheets, have been synthesized by a facile hydrothermal reaction between Mn(CH₃COO)₂·4H₂O and commercial V₂O₅. The synthesized products are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The influences of synthetic parameters, such as, reaction time, temperature and medium, on the morphologies of the resulting products have been investigated. As the reaction temperatures increase from 120 °C to 180 °C, MnV₂O₆ nanorods and nanobelts are obtained, respectively. The time-dependent experimental results at 180 °C reveal that the sizes of MnV₂O₆ nanobelts increase gradually with the reaction proceeding. Interestingly, as the reaction is carried out with the aid of H₂O₂ solution, flower-like MnV₂O₆ nanosheets are formed.     

Characterization of MMoO4 (M = Ba, Sr and Ca) with different morphologies prepared using a cyclic microwave radiation

Scheelite molybdates (MMoO₄, M = Ba, Sr and Ca) were successfully prepared by the reactions of M(NO₃)₂·2H₂O and Na₂MoO₄·2H₂O in propylene glycol and NaOH using a microwave radiation. The phases were detected using XRD and SAED. TEM analysis revealed the presence of micro-sized bi-pyramids with a square base, nano-sized particles in clusters, and dispersed nano-sized particles for BaMoO₄, SrMoO₄ and CaMoO₄, respectively. Diffraction patterns of the bi-pyramids were simulated, and are in accord with the experimental results. Raman and FTIR spectra provide the evidence of scheelite structure with Mo-O stretching vibration in MoO₄²⁻ tetrahedrons at 742-901 cm^− 1.     

A facile hydrothermal route to spinel CoCo2O4 nanotubes and porous nanostructures without assisted surfactants and templates

Spinel CoCo₂O₄ nanotubes and porous nanostructures have been synthesized by a novel hydrothermal method from Co(NO₃)₂·6H₂O in mixtures of ammonia and cyclohexane at 220 °C. The morphology and phase of CoCo₂O₄ can be controlled by adjusting the experimental parameters that include the Co²⁺ concentration and the volume ratio of ammonia to cyclohexane. X-ray diffraction and transmission electron microscopy analyses were used to characterize the products. The formation mechanisms of CoCo₂O₄ nanostructures is proposed in detail. The electrochemical properties of the as-prepared samples have been investigated.     

Hydrogen peroxide-assisted hydrothermal synthesis of hierarchical CuO flower-like nanostructures

Hierarchical CuO nanostructures were synthesized through a hydrogen peroxide-assisted hydrothermal route in which Cu(OH)₂ was the copper source. The CuO nanostructures were composed of numerous nanobelts that radiated from the center of the nanostructure and formed a flower-like shape with a diameter of 5-10 μm. The nanobelts had lengths of 2.5-5 μm and widths of 150-200 nm. The H₂O₂ concentration directly influenced the product morphology. As the concentration of H₂O₂ increased, the length and width of the nanobelts increased and the quantity of the nanobelts decreased. The possible formation mechanism of hierarchical CuO flower-like nanostructures was presented.     

Synthesis of hierarchical barium tungstate corns and their shape evolution process

Barium tungstate nanocorns with lengths of 200-800 nm and with diameters of 20-50 nm in the middle section were synthesized by a facile stepwise solution-phase method. Various comparison experiments showed that several experimental parameters, such as the volume ratio of DMF/H₂O, and the quantity of urea and CTAB, played important roles for the morphological control of BaWO₄ nanostructures. A possible mechanism is offered for the formation of the hierarchical nanostructures. The obtained samples are characterized by means of X-ray diffraction, energy dispersion X-ray spectrometry, scanning electron microscopy, and transmission electron microscopy.     

Molten salt synthesis of barium molybdate and tungstate microcrystals

Pure microcrystalline barium molybdate BaMoO₄ and barium tungstate BaWO₄ materials were prepared by molten flux reaction using alkali metal nitrates as reaction media. The obtained crystals have rhombic shape and expose mostly (111) crystallographic planes. Their mean size depends on the flux temperature and the nature of the alkali metal cation. Monomeric molybdate and tungstate used as precursors yield target products already at 673 K whereas if polymerized ammonium oxosalts were used, then higher temperatures were necessary to obtain barium salts. The optimal temperature for the preparation of pure crystals with well defined shape was found to be near 773 K. UV–visible spectra have been measured to precise energy gaps in these important d⁰ transition metal compounds. The values of Eg for these two mixed oxides are 4.3 eV for BaMoO₄ and 3.8 eV for BaWO₄. Such values contradict to what can be expected from the known data on their structure and the relative electronegativity of W and Mo ions. The possible explanations of this observation are commented.     

Microwave synthesis of SrCO3 one-dimensional nanostructures assembled from nanocrystals using ethylenediamine additive

One-dimensional SrCO₃ nanostructures assembled from nanocrystals have been successfully synthesized by a microwave-assisted aqueous solution method at 90 °C using Sr(NO₃)₂, (NH₄)₂CO₃ and ethylenediamine (C₂H₈N₂). Our experiments show that the microwave heating time plays an important role in the size and morphology of SrCO₃. A rational mechanism based on the oriented attachment self-assembly is proposed for the formation of SrCO₃ nanostructures. The products were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and selected-area electron diffraction (SAED). This method is simple, fast, low-cost and suitable for large-scale production of SrCO₃ nanostructures with different morphologies. We expect that this method may be extended to the preparation of nanostructures of other kinds of carbonates.     

Novel flower-like (Bi(Bi2S3)9I3)2/3 nanostructure as efficient photocatalyst for photocatalytic desulfurization of benzothiophene under visible light irradiation

Here, we report the preparation of hierarchical flower-like (Bi(Bi₂S₃)₉I₃)_2/3 nanostructures that acts as a strong photocatalyst in the desulfurization of benzothiophene. We optimized the reaction time, type of capping agent and reflux temperature to tune the shape of porous flower-like (Bi(Bi₂S₃)₉I₃)_2/3 nanostructures to achieve the highest desulfurization performance. We investigated the characteristic shape, size, purity, and optical response of the flower-shape nanostructures using XRD, EDS, FESEM, UV–Vis-DRS analysis. The flower-like (Bi(Bi₂S₃)₉I₃)_2/3 nanostructures showed a significant photocatalytic property in desulfurization of benzothiophene as a model fuel. The hierarchical flower-like (Bi(Bi₂S₃)₉I₃)_2/3 photocatalyst with an energy gap of 1.15 eV, exhibits a 92% photocatalytic desulfurization performance after 2 h of visible light irradiation. The (Bi(Bi₂S₃)₉I₃)_2/3 nanostructures show a high photocatalytic reproducibility after 4 rounds of exposure. We proposed a photo-oxidation mechanism based on the active species scavenging, which revealed the role of photo-produced h⁺ and O₂^? species as essential in the photocatalytic desulfurization process. These findings provide a new prospect and design strategy for the development of efficient photocatalysts in desulfurization process.     

Hydrothermal-polyol route to synthesis of β-Ni(OH)2 and NiO in mixed solvents of 1,4-butanediol and water

The β-Ni(OH)₂ with flower-like morphology assembled from nanosheets has been successfully synthesized by a hydrothermal-polyol method from Ni(CH₃COO)₂·4H₂O in mixed solvents of 1,4-butanediol and water at 200 °C for 24 h. The NiO with similar morphology was obtained by a simple thermal decomposition of the precursor (β-Ni(OH)₂) at 400 °C for 3 h in air. The products were characterized by X-ray powder diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), thermogravimetric analysis (TG) and differential scanning calorimetric analysis (DSC). We expect that this hydrothermal-polyol method may be extended to the preparation of nanostructures of other kinds of metal oxides.     

Synthesis and characterization of novel nanorod superstructures and twin octahedral morphologies of WO3 by hydrothermal treatment

Controlled WO₃ morphologies, such as nanorods and octahedral structures, were synthesized by the hydrothermal technique using sulfate salts based structure directing agents (SDAs). The role of the sulfate salts’ cation in controlling the shape, size and phase of WO₃ nanomaterials was investigated by choosing sulfate salts whose cations are from d-bloc elements (FeSO₄, (NH₄)₂Fe(SO₄)₂, CoSO₄, CuSO₄, ZnSO₄), an alkaline earth metal (MgSO₄) and a non-metal ((NH₄)₂SO₄). In addition chloride (MnCl₂) and acetate (Zn(CH₃CO₂)₂) anion based SDAs were also used in order to clarify the role of sulfate ions in the growth of WO₃ nanostructures. We controlled the pH of the reaction medium with oxalic acid. The obtained WO₃ samples were investigated by SEM, micro-Raman, and XRD. At pH = 1, the WO₃ samples exhibit novel superstructures consisting of aligned hexagonal nanorods, whereas at pH = 5.25, novel twin octahedral morphology with a cubic structure is obtained. The results demonstrate that the phase and morphology change is influenced by the pH and both the anion and the cation of the SDA. A growth mechanism for the obtained novel WO₃ morphologies is presented.     

Hydrothermal synthesis of different 3D SnO2 nanostructures and their gas-sensing properties

Different morphologies of 3D SnO₂ nanostructures, including sphere-like, net-like, and flower-like, have been successfully synthesised via a facile hydrothermal method. The products were characterized by X-ray diffraction and scanning electron microscopy. The possible growth mechanism of different SnO₂ nanostructures was discussed in detail. We found that the citric acid and PEG play significant roles in synthesizing the flower-like and net-like nanostructures. Furthermore, the gas-sensing properties of the samples were investigated towards the reducing ethanol gas. The results indicate that the flower-like and net-like SnO₂ show larger gas sensing properties than sphere-like SnO₂.     

Cu2S nanostructures prepared by Cu-cysteine precursor templated route

A facile Cu-cysteine precursor templated route for the synthesis of Cu₂S nanowires, dendritic-like and flowerlike nanostructures is reported. The Cu-cysteine precursors are prepared through the reaction between Cu²⁺, l-cysteine and ethanolamine at room temperature, and the morphologies of Cu-cysteine precursors can be controlled by adjusting the molar ratio of l-cysteine to Cu²⁺. The Cu-cysteine precursors are used as both templates and source materials for the subsequent preparation of polycrystalline Cu₂S nanostructures by thermal treatment, and the morphologies of the precursors can be well preserved after the thermal transformation to Cu₂S nanostructures. The samples are characterized using X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, energy dispersive spectroscopy and Fourier transform infrared spectroscopy.