Fabrication and efficient photocatalytic degradation of methylene blue over CuO/BiVO4 composite under visible-light irradiation

CuO/BiVO₄ composite photocatalysts were prepared by solution combustion synthesis method and impregnation technique. X-ray diffraction, X-ray photoelectron spectroscopy, field-emission scan electron microscopy and UV-vis diffusion reflectance spectra were used to identify the physical properties and photophysical properties of CuO/BiVO₄ composite photocatalysts. The photocatalysts exhibit the enhanced photocatalytic properties for degradation of methylene blue under visible-light (λ > 420 nm). The mechanism of improved photocatalytic activity is also discussed.     

Synthesis of BaTiO3 nanoparticle/poly(2-hydroxyethyl methacrylate) hybrid nanofibers via electrospinning

BaTiO₃ nanoparticle/poly(2-hydroxyethyl methacrylate) (PHEMA) hybrid nanofibers were fabricated from an in situ synthesized BaTiO₃ nanoparticle/polymer hybrid by electrospinning. The bulk hybrid for nanofibers was synthesized through the in situ hydrolysis of Ba–Ti alkoxide modified with 2-vinyloxyethanol and subsequent copolymerization with HEMA monomer. IR and ¹³C NMR spectra showed the formation of polymer matrix. The molecular weights of BaTiO₃ nanoparticle/PHEMA hybrid for spinning were 1.3 × 10⁵ for 20 equiv. PHEMA and 5.7 × 10⁵ for 30 equiv. PHEMA. The crystallite size of BaTiO₃ particles in the hybrid was 4.5 nm according to the Scherrer equation. The diameter of BaTiO₃ nanoparticle/PHEMA hybrid nanofibers ranged from 500 nm to 1 μm. A field stress–strain curve was observed for the BaTiO₃ nanoparticle/PHEMA hybrid nanofiber.     

Size reduction of WO3 nanoparticles by ultrasound irradiation and its applications in structural nanocomposites

The porous WO₃ (pore size 2–5 nm) nanoparticles were synthesized using a high intensity ultrasound irradiation of commercially available WO₃ nanoparticles (80 nm) in ethanol. The high resolution transmission electron microscopic (HRTEM) and X-ray studies indicated that the 2–5 nm uniform pores have been created in commercially available WO₃ nanoparticles without much changing the initial WO₃ nanoparticles (80 nm) sizes. The nanocomposites of WO₃/SC-15 epoxy were prepared by infusion of 1 wt.%, 2 wt.% and 3 wt.% of porous WO₃ nanoparticles into SC-15 epoxy resin by using a non-contact (Thinky) mixing technique. Finally the neat epoxy and nanocomposites were cured at room temperature for about 24 h in a plastic rectangular mold. The cured epoxy samples were removed and precisely cut into required dimensions and tested for their thermal and mechanical properties. The HRTEM and SEM studies indicated that the sonochemically modified porous WO₃ nanoparticles dispersed more uniformly over the entire volume of the epoxy (without any settlement or agglomeration) as compared to the unmodified WO₃/epoxy nanocomposites.     

Structural and magnetic properties of Mn nanoparticles prepared by arc-discharge

Mn nanoparticles are prepared by arc discharge technique. MnO, α-Mn, β-Mn, and γ-Mn are detected by X-ray diffraction, while the presence of Mn₃O₄ and MnO₂ is revealed by X-ray photoelectron spectroscopy. Transmission electron microscopy observations show that most of the Mn nanoparticles have irregular shapes, rough surfaces and a shell/core structure, with sizes ranging from several nanometers to 80 nm. The magnetic properties of the Mn nanoparticles are investigated between 2 and 350 K at magnetic fields up to 5 T. A magnetic transition occurring near 43 K is attributed to the formation of the ferrimagnetic Mn₃O₄. The coercivity of the Mn nanoparticles, arising mainly from Mn₃O₄, decreases linearly with increasing temperature below 40 K. Below the blocking temperature T_B ≈ 34 K, the hysteresis loops exhibit large coercivity (up to 500 kA/m), owing to finite size effects, and irreversibility in the loops is found up to 4 T, and magnetization is not saturated up to 5 T. The relationship between structure and the magnetic properties are discussed.     

The interaction of oxygen with high loaded Ru/γ-Al2O3 catalyst

The interaction of oxygen with the Ru/γ-Al₂O₃ catalyst comprising metal particle with sizes of 1-16 nm, was examined over a temperature range 20-400 °C. The catalyst loaded with 10.8 wt.% Ru was prepared by incipient wetness from RuCl₃ precursor. The structure of the Cl-containing catalyst and the catalyst after elimination Cl⁻ ions was characterized using H₂ and O₂ chemisorption, O₂ uptake, BET, XRD and TEM. The Cl⁻ ions in the catalyst decreased the H₂ and O₂ chemisorption capacity of Ru and caused large discrepancies between the mean particle size calculated from gas chemisorption and from TEM. Exposure to O₂ at 100-200 °C caused oxidation of small Ru particles, while larger particles were covered with very thin Ru_xO_y skin (undetected by XRD and TEM). The O/Ru ratio increased up to 200 °C implying high affinity of the small Ru particles to oxygen. Oxidation at 250 °C led to the formation of poorly crystalline RuO₂ particles with a mean size of 4 nm, and coverage of large Ru particles with 1.6 nm thick oxide layer. At 300 and 400 °C crystallization of the RuO₂ phase, as well as significant agglomeration of oxide particles was observed. However, even at 400 °C, metallic Ru was detected by XRD, TEM and SAED suggesting that large metal particles were not fully oxidized under the used conditions. Also, the O₂ uptake at 400 °C was lower than expected for oxidation of Ru metal to RuO₂. For the catalyst after elimination Cl ions the O₂ uptake (O/Ru ratio = 1.50) was higher, than for sample with large amount of Cl ions (O/Ru ratio = 1.34), indicating that the presence of Cl inhibits ruthenium oxidation in the Ru/Al₂O₃ catalyst.     

Modification and optimization of nano-crystalline Al2O3 combustion synthesis using Taguchi L16 array

Nanocrystalline Al₂O₃ powders have been synthesized by combustion method using 8 new fuels. The effectiveness of important factors on the production of nanopowders was investigated and optimized using Taguchi L₁₆ array design. The products were characterized by XRD, BET, TGA, EDX, FESEM, and TEM analyses. Results demonstrated that the alumina nanoparticles had crystallite sizes between 8.31 nm and 13.54 nm. The optimized sample had the specific surface area of 72 m²/g and crystallite size of 7.25 nm. The synthesis of γ-alumina was modified in order to achieve higher specific surface area (122.63 m²/g). A nano-network of alumina powders woven by alumina nano-fibers has been fabricated successfully by modified combustion synthesis. The length and diameter of fibers were about 160 nm and 10 nm respectively.     

Preparation of cobalt-zinc ferrite (Co0.8Zn0.2Fe2O4) nanopowder via combustion method and investigation of its magnetic properties

Cobalt-zinc ferrite (Co_0.8Zn_0.2Fe₂O₄) was prepared by combustion method, using cobalt, zinc and iron nitrates. The crystallinity of the as-burnt powder was developed by annealing at 700 °C. Crystalline phase was investigated by XRD. Using Williamson-Hall method, the average crystallite sizes for nanoparticles were determined to be about 27 nm before and 37 nm after annealing, and residual stresses for annealed particles were omitted. The morphology of the annealed sample was investigated by TEM and the mean particle size was determined to be about 30 nm. The final stoichiometry of the sample after annealing showed good agreement with the initial stoichiometry using atomic absorption spectrometry. Magnetic properties of the annealed sample such as saturation magnetization, remanence magnetization, and coercivity measured at room temperature were 70 emu/g, 14 emu/g, and 270 Oe, respectively. The Curie temperature of the sample was determined to be 350 °C using AC-susceptibility technique.     

Synthesis and characterization of K2NiF4-type CaLnCoO4 (Ln = Sm and Gd)

K₂NiF₄-type CaLnCoO₄ (Ln = Sm and Gd) has been synthesized at 1173 or 1223 K in air using citric acid (CA) and ethylene glycol (EG). CaLnCoO₄ (Ln = Sm and Gd) has an orthorhombic structure with the space group Bmab. The average particle sizes are approximately 300 nm for CaSmCoO₄ and approximately 170 nm for CaGdCoO₄, respectively. The global instability index (GII) indicates that the crystal structure of CaGdCoO₄ is more stable than that of CaSmCoO₄. CaLnCoO₄ (Ln = Sm and Gd) is a p-type semiconductor and shows paramagnetic behavior above 5 K. The 1/χ-T curve of CaSmCoO₄ deviates from the Curie-Weiss law, whereas the 1/χ-T curve of CaGdCoO₄ follows the Curie-Weiss law in the temperature range of 5 ≤ T ≤ 300 K. From the values of the observed effective magnetic moment (μ_eff) of CaLnCoO₄ (Ln = Sm and Gd), it is considered that the spin state of the Co³⁺ ion is low.     

Large-scale synthesis of CuS hexaplates in mixed solvents using a solvothermal method

Large-scale covellite CuS hexaplates were successfully synthesized by the 200 °C solvothermal reactions of CuCl₂.2H₂O and (NH₄)₂S in C₂H₅OH-H₂O mixed solvents containing HCOOH as a pH stabilizer, including different amounts and molecular weights (MWs) of polyethylene glycol (PEG). By using XRD and SAED, CuS (hcp) was detected. XRD peaks of the product, synthesized in a solution containing 5 g PEG6000 and 1.5 ml HCOOH for 5 h, are in accordance with those of the simulation and database. The (110) peak shows the preferential growth, corresponding to the hexaplates, characterized using SEM, TEM and HRTEM. CuS hexaplates with the (100) and (010) lattice planes at an angle of 120° were detected on the flat surface, and the (002) lattice plane on the edge. UV-vis absorption edge was detected at 610 nm (2.03 eV), and the PL emission at 361 nm (3.43 eV). Phase and morphology formations were also explained according to the experimental results.     

Mass-synthesized anatase titania nanocrystals with tunable size and shape via sol-gel in organic solvents with adsorbing ligands

High-quality anatase titania (TiO₂) nanoparticles, nanowires, and nanorods have been mass-synthesized by the modified sol-gel method in the saturated fatty alcohol, acid, and amine systems with adsorbing ligands, respectively. These obtained quasi-spherical TiO₂ nanoparticles showed the mean size of 16.5 nm with a narrow size-distribution. These resulting TiO₂ nanowires had the uniform diameter of 3.8 nm with the length range of 80-180 nm, and TiO₂ nanorods had the uniform diameter of 7.5 nm with the length range of 40-70 nm, respectively. We demonstrated that the shapes, sizes and morphology of these anatase TiO₂ nanocrystals could be controlled systematically by adjusting certain reaction parameters, such as the kind of organic solvents, the alkyl length of organic solvents, and the reaction time. It has been found that the shape of the products was primarily determined by the kind of organic solvents. However, their sizes, size-distributions, and morphology could be controlled by adjusting the alkyl length of organic solvents and the reaction time. Based on the analysis of all experiment results, we have investigated the growth mechanism of these TiO₂ nanocrystals with the different shape. Meanwhile, this synthetic method can be extended further for the preparation of other oxides nanocrystals.     

Preparation of In2O3 octahedrons by heating InCl3 aqueous solution on the Si substrate

In₂O₃ octahedrons have been synthesized by heating InCl₃ aqueous solution on the Si substrate at 400-900 °C for 2 h. The average size of In₂O₃ octahedrons is decreased by increasing the heating temperature. The In₂O₃ octahedrons are single-crystalline with the body-centered cubic structure and have controllable sizes in the range of 0.7-1.0 μm. A possible mechanism was also proposed to account for the formation of In₂O₃ octahedrons. A strong photoluminescence with a peak at 458 nm was observed from the In₂O₃ octahedrons at room temperature. This emission can be attributed to oxygen vacancies and indium-oxygen vacancy centers.     

Preparation and characterization of organic-inorganic poly(ethylene glycol)/WS2 nanocomposite

Layered nanocomposite PEG/WS₂, intercalating oligomeric poly(ethylene glycol) (PEG6000) into the tungsten disulfide host galleries, was synthesized using the exfoliation-adsorption technique. X-ray diffraction revealed that the intercalated oligomer within the host galleries is in a double-layer arrangement with an interlayer expansion of about 8.8 Å. The optimum conditions were explored to prepare the single-phase product with a composition of Li_0.12(PEG)_1.51WS₂. Thermal analyses suggested that the resulting material shows good thermal stability, with the decomposition of the interacted oligomeric chains within the disulfide galleries occurring at around 258 °C. Despite high conductivity of the host material, those of the PEG/WS₂ nanocomposite were found to be high in the order of 1 × 10⁻² S cm⁻¹ at ambient temperature, resulted from the host guest-host charge transfers.     

A novel broadband emission phosphor Ca2KMg2V3O12 for white light emitting diodes

A novel broadband emission phosphor Ca₂KMg₂V₃O₁₂ was first synthesized by solution combustion method. The X-ray diffraction showed that Ca₂KMg₂V₃O₁₂ phase can be obtained at 600-900 °C through combustion route. The crystal structure of this material was refined by Rietveld method using powder X-ray diffraction. It crystallizes in cubic system and belongs to space group Ia3d with z = 8, a = 0.12500 nm. The excitation band of Ca₂KMg₂V₃O₁₂ peaks at 320 nm in a region between 260 nm and 425 nm, and the emission spectrum exhibits an intense band centered at about 528 nm covering from 400 nm to 800 nm. The colour coordinates of samples prepared at different ignition temperatures are in a range of x = 0.323-0.339, y = 0.430-0.447.     

Synthesis and characterization of (Na0.85K0.15)0.5Bi0.5TiO3 ceramics by different methods

The (Na_0.85K_0.15)_0.5Bi_0.5TiO₃ (BNKT) powders were synthesized by solid-state method, sol-gel method and stearic acid method. Microstructure, piezoelectric and dielectric properties of the ceramics were investigated. Attempts had been made to understand the reaction processes by using thermo gravimetric (TG) and differential scanning calorimetry (DSC). The BNKT powders have a perovskite structure with average crystallite sizes of 168 nm, 85 nm and 79 nm, corresponding to the solid-state method, the sol-gel method and the stearic acid method, respectively. The ceramics derived from the powder synthesized by sol-gel method presents the most homogeneous microstructure and largest grain size (5-7 μm). The effects of average crystallite size on microstructures and electric properties of the BNKT ceramics were investigated. Both the piezoelectric properties and dielectric properties were enhanced with the increase of grain size.     

Photocatalytic degradation of organic dyes by mesoporous nanocrystalline anatase

Mesoporous nanocrystalline anatase was prepared via EISA employing P123 and CTAB as structure directing agents. The resultant mesoporous crystalline phases exhibited specific surface areas as high as ∼150 m² g⁻¹, average unimodal pore sizes of ∼3 nm and ∼6 nm, and average crystallite size of ∼10 nm; and were used as photocatalysts for the UV degradation of methylene blue, methyl orange, methyl red and rhodamine 6G. The mesoporous anatase phases photodegraded MB, MO and MR ∼2–3 times faster than conventional nanocrystalline anatase and showed limited photocatalytic activity for rhodamine 6G.     

Electronic structure and photocatalytic water splitting of lanthanum-doped Bi2AlNbO7

Bi_2−xLa_xAlNbO₇ (0 ≤ x ≤ 0.5) photocatalysts were synthesized by the solid-state reaction method and characterized by powder X-ray diffraction (XRD), infrared (IR) spectra and ultraviolet-visible (UV-vis) spectrophotometer. The band gaps of the photocatalysts were estimated from absorption edge of diffuse reflectance spectra, which were increased by the doping of lanthanum. It was found from the electronic band structure study that orbitals of La 5d, Bi 6p and Nb 4d formed a conduction band at a more positive level than Bi 6p and Nb 4d orbitals, which results in increasing the band gap. Photocatalytic activity for water splitting of Bi_1.8La_0.2AlNbO₇ was about 2 times higher than that of nondoped Bi₂AlNbO₇. The increased photocatalytic activity of La-doped Bi₂AlNbO₇ was discussed in relation to the band structure and the strong absorption of OH groups at the surface of the catalyst.     

Facile fabrication of ZrO2 hollow porous microspheres with yeast as bio-templates

ZrO₂ hollow porous microspheres have been fabricated successfully using living yeast cells as bio-templates through a facile ageing process at lower crystallizing temperature. XRD, SEM, FT-IR and N₂ adsorption-desorption were used to characterize ZrO₂ hollow microspheres. The results showed that the inorganic-organic hybrid hollow microspheres were fabricated at 100 °C and ZrO₂ hollow microspheres with tetragonal phase and porous structure were obtained at 300 °C. The crystallization temperature of ZrO₂ decreased obviously due to the inducting of bio-molecules. The as-prepared hollow microspheres are approximately ellipsoid. The shells of these hollow microspheres are porous, which are composed of some nanoparticles with size of ∼20 nm. The formation mechanism of ZrO₂ hollow microspheres was proposed and discussed tentatively.     

Chemical synthesis of environment-friendly nanosized yellow titanate pigments

As yellow pigments, nanosized rutile structured Ni_0.1W_0.1Ti_0.8O₂ and priderite structured BaNiTi₇O₁₆ have been prepared through pyrolysis of precursor solution containing nickel nitrate, dimethyl tungstate, titanium oxalate, triethanolamine (TEA) for the former composition and barium nitrate, nickel nitrate, titanium oxalate, TEA for the later composition, respectively. In the reaction, TEA acts to minimize the agglomeration in the products through formation of a highly branched polymeric framework, which anchors the metal ions for producing nanocrystalline powders. The rutile and priderite structured titanates obtained on heat-treatment of the precursor powders at 800 °C and 850 °C, respectively, have been characterized by XRD, TGA-DTA, BET surface area measurement, UV-vis spectroscopy, CIE L^*a^*b^* colour parameter measurements, TEM and HRTEM. XRD reveals the purity of the resulting rutile and priderite phases. Their crystallite sizes, average particle sizes and specific surface areas determined from XRD, TEM, and BET surface area measurement are found to be in the range between 25 nm and 30 nm, 25-45 nm and 100-120 m²/g, respectively, for both compositions.     

Photocatalytic hydrogen production over Na2Ti2O4(OH)2 nanotube sensitized by CdS nanoparticles

Na₂Ti₂O₄(OH)₂ nanotubes were obtained by hydrothermal reaction of TiO₂ with concentrated NaOH solution. CdS nanoparticles were then decorated on Na₂Ti₂O₄(OH)₂ nanotubes through partial ion-exchange method. The composite photocatalysts were characterized by X-ray diffraction (XRD), ultraviolet-visible spectra (UV-vis), transmission electron microscope (TEM), etc. The results showed that CdS nanoparticles of 5-6 nm were anchored on the surface of the Na₂Ti₂O₄(OH)₂ nanotubes. Under irradiation of visible light (λ ≥ 430 nm), the prepared CdS/Na₂Ti₂O₄(OH)₂ showed high photoactivity for hydrogen production.     

Novel Dy-doped Ca2Gd8(SiO4)6O2 white light phosphors for Hg-free lamps application

The luminescent properties of Ca₂Gd_8(1−x)(SiO₄)₆O₂:xDy³⁺ (1% ≤ x ≤ 5%) powder crystals with oxyapatite structure were investigated under vacuum ultraviolet excitation. In the excitation spectrum, the peaks at 166 nm and 191 nm of the vacuum ultraviolet region can be assigned to the O²⁻ → Gd³⁺, and O²⁻ → Dy³⁺ charge transfer band respectively, which is consistent with the theoretical calculated value using Jφrgensen's empirical formula. While the peaks at 183 nm and 289 nm are attributed to the f-d spin-allowed transitions and the f-d spin-forbidden transitions of Dy³⁺ in the host lattice with Dorenbos's expression. According to the emission spectra, all the samples exhibited excellent white emission under 172 nm excitation and the best calculated chromaticity coordinate was 0.335, 0.338, which indicates that the Ca₂Gd₈(SiO₄)₆O₂:Dy³⁺ phosphor could be considered as a potential candidate for Hg-free lamps application.