Hydrogenation of p-chloronitrobenzene on Ni–B Nanometal Catalysts

A series of Ni–B catalysts were prepared by mixing nickel acetate in 50% ethanol/water or methanol/water solution. The solution of sodium borohydride (1 M) in excess amount to nickel was then added dropwise into the mixture to ensure full reduction of nickel cations. The mol ratio of boron to nickel in mother solution was 3 to 1. The effects of preparation conditions such as temperature, stirring speed, and sheltering gas on the particle size, surface compositions, electronic states of surface atoms and catalytic activities of the Ni–B catalysts were studied. Ranel nickel catalyst was included for comparison. These catalysts were characterized by N₂ sorption, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. The catalysts were tested for liquid phase hydrogenation of p-chloronitrobenzene. All of the catalysts prepared in this study had nanosized particles. The preparation condition has significant influence on the particle size and surface compositions of the catalyst. The Ni–B catalyst was passivated by boron; therefore it was more stable than Raney nickel and did not catch fire after exposure to air. The catalysts prepared under N₂ flow could suppress the oxidation of Ni by the dissolved oxygen in water and had metallic state of nickel. The catalyst prepared with vigorous stirring at 25°C under N₂ stream yielded the smallest particles and resulted in the highest activity. It was much more active than the Raney nickel catalyst. The reaction condition also has pronounced effect on the hydrogenation activity. Using methanol as the reaction solvent increased p-chloronitrobenzene conversion to a large extent, compared to that using ethanol as the reaction medium. The selectivity of main product (p-chloroaniline) was greater than 99% on all of the Ni–B catalysts.     

Effects of precursor types of Fe and Ni components on the properties of NiFe2O4 powders prepared by spray pyrolysis

The effects of the precursor types of Ni and Fe components on the morphology, mean size, and magnetic property of NiFe₂O₄ powders prepared by spray pyrolysis from the spray solution, with citric acid were studied. The precursor powders with hollow and thin wall structure turned to the nano-sized NiFe₂O₄ powders after post-treatment at a temperature of 800 °C. The nickel ferrite powders obtained from the spray solution with ferric chloride had nanometer sizes and narrow size distributions irrespective of the types of nickel precursor. The nickel ferrite powders obtained from the spray solution with ferric nitrate and nickel chloride also had nanometer size and narrow size distribution. The saturation magnetizations of the NiFe₂O₄ powders changed from 37 to 42 emu/g according to the types of the Fe and Ni precursors. The saturation magnetizations of the NiFe₂O₄ powders increased with increasing the Brunauer-Emmett-Teller (BET) surface areas of the powders.     

Synthesis and characterization of nanocrystalline titanium nitride powder from rutile and anatase as precursors

In this research nanosized titanium nitride powder was synthesized through reaction of titanium oxide with ammonia gas. The reaction was carried out at a very slow heating rate. Two different TiO₂ starting powders contained rutile and anatase phase and differed in initial particle size and surface area. The crystallite size of TiN powders synthesized at 1000 °C was obtained about 40 nm for anatase sample. Surface area and particle size were found to be 19 m²/g, 70 nm for rutile sample and 31 m²/g, 39 nm for anatase sample, respectively. The rutile sample showed an increasing trend in surface area during conversion to the nitride, whilst the anatase sample followed an adverse trend. TiN powder synthesized from anatase had the highest surface area and smallest particle size due to the specification of initial precursor.     

Effect of calcination temperature on porous titania prepared from industrial titanyl sulfate solution

Porous titania with anatase phase was prepared via thermal hydrolysis of industrial titanyl sulfate solution, and subsequent calcination at different temperature. The as-prepared powders were characterized by TG, DSC, XRD, particle size distribution test, N₂ adsorption-desorption isotherm and SEM. Raising calcination temperature could accelerate the crystal growth, enlarge its specific surface area, pore diameter, and improve its photocatalytic activity. While too high temperature could destroy the pore structure even collapse. The optimal calcination temperature is 550 °C, and the obtained sample showed good thermal stability and high photocatalytic activity, with specific surface area of 189.3 m²/g and higher degree of crystallinity, and its photocatalytic degradation rate of methylene blue was of 95.76%.     

Characterization of SiC and Si<Subscript>3</Subscript>N<Subscript>4</Subscript> nanoparticles and their aqueous dispersions

Nanoparticles of SiC and Si₃N₄ were previously used to obtain electroless NiP/particles nanocomposites. The incorporation process was very different, depending on the particle: SiC tended to agglomerate and had a high incorporation level; Si₃N₄ particles were not aggregated, but their incorporation level was very low. To try to explain these differences, the particles and their aqueous dispersions were characterized. Although the as-received products were both oxidized and of the identical mean size, results showed that the size distributions and the surface oxidation products were rather different. The zeta potential in water dispersions was similar and negative for both particles but, as the electrolyte ions were introduced, it showed a different evolution: nitride particles retained a small negative charge and carbide was almost uncharged. The overall results obtained in this study explain the different behavior of both ceramic particles and provide possible solutions to improve their co-deposition with nickel.     

Immobilized TiO<Subscript>2</Subscript> nanoparticles produced by flame spray for photocatalytic water remediation

Anatase/rutile mixed-phase titanium dioxide (TiO₂) photocatalysts in the form of nanostructured powders with different primary particle size, specific surface area, and rutile content were produced from the gas-phase by flame spray pyrolysis (FSP) starting from an organic solution containing titanium (IV) isopropoxide as Ti precursor. Flame spray-produced TiO₂ powders were characterized by means of X-ray diffraction, Raman spectroscopy, and BET measurements. As-prepared powders were mainly composed of anatase crystallites with size ranging from 7 to 15 nm according to the synthesis conditions. TiO₂ powders were embedded in a multilayered fluoropolymeric matrix to immobilize the nanoparticles into freestanding photocatalytic membranes. The photocatalytic activity of the TiO₂-embedded membranes toward the abatement of hydrosoluble organic pollutants was evaluated employing the photodegradation of rhodamine B in aqueous solution as test reaction. The photoabatement rate of best performing membranes significantly overcomes that of membranes produced by the same method and incorporating commercial P25-TiO₂.     

Effect of small particle sizes on the measured density of nanocrystalline powders of nonstoichiometric tantalum carbide TaC<Subscript> <Emphasis Type="Italic">y</Emphasis> </Subscript>

Nanocrystalline powders of the nonstoichiometric tantalum carbide TaC_y (0.81 ≤ y ≤ 0.96) with an average particle size in the range from 45 to 20 nm have been prepared using high-energy ball milling of coarse-grained powders. The density of the initial coarse-grained and prepared nanocrystalline powders of TaC_y has been measured by helium pycnometry. The sizes of particles in tantalum carbide powders have been estimated using the X-ray diffraction analysis and the Brunauer–Emmett–Teller (BET) method. The density of TaC_y nanopowders measured by helium pycnometry is underestimated as compared to the true density due to the adsorption of helium by the highly developed surface of the nanocrystalline powders. It has been shown that the difference between the true and measured densities is proportional to the specific surface area or is inversely proportional to the average particle size of the nanopowders. The large difference between the true and measured pycnometric densities indicates a superhydrophobicity of the tantalum carbide nanopowders.     

Induction heating studies of magnetite nanospheres synthesized at room temperature for magnetic hyperthermia

An investigation of the synthesis of Fe₃O₄ nanopowders by the co-precipitation method is reported from aqueous and ethanol mediums. X-ray diffraction (XRD), transmission electron microscopy (TEM) and vibrating sample magnetometer are utilized to study the effect of variation of synthesis conditions on the crystal structure, crystallite size, microstructure and magnetic properties of the formed powders. The XRD analysis showed that the crystalline Fe₃O₄ phase was formed at Fe³⁺/Fe²⁺ molar ratio 2.0 prepared at room temperature for 1 h at pH 10. The crystallite size was in the range between 8 and 11 nm. TEM micrographs showed that the particles appeared as nanospheres. Superparamagnetic nanoparticles with low coercivity and remanence magnetization were achieved. Heating properties of the nanosphere samples in an alternating magnetic field at 160 KHz were evaluated. An excellent heating efficiency for the sample prepared in ethanol medium is a result of more relaxation losses occurring due to its small particle size.     

Comparative study of LiNi0.05Mn1.95O4 powders prepared by different materials for Li-ion battery

LiNi_0.05Mn_1.95O₄ powders were prepared by manganese tetraoxide (MTO) and electrolytic manganese dioxide (EMD). The phase identification, surface morphology, and electrochemical properties of the prepared powders were studied by X-ray diffraction, scanning electron microscopy, cyclic voltammetry, and galvanostatic charge?Cdischarge experiments. Compared to LiNi_0.05Mn_1.95O₄ powders prepared by EMD, LiNi_0.05Mn_1.95O₄ powders prepared by MTO show better crystallinity. Both powders possess a typical cubic structure with uniform particle size. The specific capacity and coulombic efficiency of LiNi_0.05Mn_1.95O₄ powders prepared by MTO are higher than the one prepared by EMD. The capacity retention of LiNi_0.05Mn_1.95O₄ powders prepared by MTO cycled 30 times at room temperature and 55?°C are 98.3% and 90.6%, respectively, which are much higher than those of 86.63% and 77.7% for the one prepared by EMD. LiNi_0.05Mn_1.95O₄ powders prepared by MTO show higher specific capacity and better cycling performance than the one prepared by EMD.     

Low-temperature synthesis of nanocrystalline β-dicalcium silicate with high specific surface area

β-Dicalcium silicate (β-Ca₂SiO₄) was synthesized for the first time by a simple solution combustion method using citric acid as fuel. The influence of calcination temperature on the average crystallite size, specific surface area and morphology of the powders were investigated by X-ray diffraction technique (XRD), scanning electron microscopy (SEM) and N₂ adsorption measurements (BET). The results showed that the increase of calcination temperature from 650°C to 1100°C resulted in larger crystallite size and lower specific surface area of β-Ca₂SiO₄. The highest specific surface area could reach as high as 26.7 m²/g when the as-burnt powders were calcined at 650°C.     

Luminescent properties and the morphology of SrMoO<Subscript>4</Subscript>:Eu<Superscript>3+</Superscript> powders synthesized <Emphasis Type="Italic">via</Emphasis> combining sol-gel and solid-state route

SrMoO₄:Eu³⁺ red phosphors were prepared by combining sol-gel and solid-state route. Citric acid and ethylenediaminetetraacetic acid (EDTA), employed as the chelating agents, were added to the aqueous solutions of metal nitrates. X-ray diffraction (XRD) and photoluminescent spectra techniques (PL) were used to characterize the resultant powders. The results indicated the obtained SrMoO₄:Eu³⁺ phosphors were fine powders with a particle size of 50 nm. The effects of synthesizing conditions were also investigated and optimized, which included the synthesis temperature and the activator concentration on the luminescent intensity. Compared with SrMoO₄:Eu³⁺ phosphors prepared by Solid-state reaction SrMoO₄:Eu³⁺ phosphors prepared by combining sol-gel and solid-state route showed appropriate particle size and a higher emission intensity.     

Low-temperature hydrothermal synthesis of highly photoactive mesoporous spherical TiO2 nanocrystalline

TiO₂ microspheres with mesoporous textural microstructures and high photocatalytic activity were prepared by hydrothermal treatment of mixed solution of titanium sulfate and urea with designed time. The prepared samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and N₂ adsorption-desorption measurements. The photocatalytic activity was evaluated via the photocatalytic oxidation of acetone in air at room temperature. The results show that the hydrothermal time significantly influences on the morphology, microstructure and photocatalytic activity of the as-prepared samples. With increasing hydrothermal time, specific surface areas and pore volumes decrease, contrarily, the crystallite size and relative anatase crystallinity increase. The photocatalytic efficiency of the as-prepared samples is obviously higher than that of commercial Degussa P25 (P25) powders. Especially, the as-prepared TiO₂ powders by hydrothermal treatment for 7 h shows the highest photocatalytic activity, which exceeds that of P25 by a factor of more than 2 times.     

Evolution of structure, microstructure and hyperfine properties of nanocrystalline Fe50Co50 powders prepared by mechanical alloying

Nanostructured Fe₅₀Co₅₀ powders were prepared by mechanical alloying of Fe and Co elements in a vario-planetary high-energy ball mill. The structural properties, morphology changes and local iron environment variations were investigated as a function of milling time (in the 0-200 h range) by means of X-ray diffraction, scanning electron microscopy (SEM), energy dispersive X-ray analysis and ⁵⁷Fe Mössbauer spectroscopy. The complete formation of bcc Fe₅₀Co₅₀ solid solution is observed after 100 h milling. As the milling time increases from 0 to 200 h, the lattice parameter decreases from 0.28655 nm for pure Fe to 0.28523 nm, the grain size decreases from 150 to 14 nm, while the meal level of strain increases from 0.0069% to 1.36%. The powder particle morphology at different stages of formation was observed by SEM. The parameters derived from the Mössbauer spectra confirm the beginning of the formation of Fe₅₀Co₅₀ phase at 43 h of milling. After 200 h of milling the average hyperfine magnetic field of 35 T suggests that a disordered bcc Fe-Co solid solution is formed.     

Sintering and electrical conductivity of gadolinia-doped ceria

Bulk specimens of Ce_0.9Gd_0.1O_2-δ prepared with powders within a range of specific surface area were sintered in oxidizing, inert, and reducing atmospheres. The aim of this work is to investigate the effects of the sintering atmosphere on the microstructure and grain and grain boundary conductivities of the solid electrolyte. The lattice parameter determined by Rietveld refinement is 0.5420(1) nm, and the microstrain was found negligible in the powder materials. Specimens sintered in the Ar/4 % H₂ mixture display larger average grain sizes independent on the particle size of the starting powders. The grain and grain boundary conductivities of specimens sintered under reducing atmosphere are remarkably lower than those sintered under oxidizing and inert atmospheres. The activation energy (～0.90 eV) for total electrical conductivity remains unchanged with both the initial particle size and the sintering atmosphere.     

Structural,optical and photoelectrochemical studies on the nanodispersed titania

Nanodispersion of aggregated TiO₂ powders has been performed by microbead milling and its effect on photovoltaic performance has been investigated with dye-sensitized solar cell. Plasma-treated 30 μm-diameter zirconia beads are used to disperse the aggregated nanocrystalline TiO₂ powders in ethanolic medium. Particle size distribution, surface area, film morphology, porosity, transmittance and haze are investigated with different milling speed. Microbead milling leads to a reduction of particle size, narrow size distribution and increase of surface area. A slight crystal phase transformation from anatase to rutile is also observed after microbead milling. Optical property is found to be influenced by microbead milling speed, where transmittance increases and haze decreases with increasing milling speed. Compared with photovoltaic performance of dye-sensitized solar cells based on titania before and after microbead milling, overall conversion efficiency is substantially improved from 4.46% to 6.31% after microbead milling at 2490 rpm for 90 min, corresponding to 42% increment, which is mainly due to a noticeable increase in photocurrent density, associated with highly dispersed characteristics. According to the photocurrent and photovoltage transient spectroscopic study, time constant for electron transport is hardly affected, while that for recombination is slightly decreased due to the increased surface area by nanodispersion.     

Synthesis and magnetic characterization of nickel ferrite nanoparticles prepared by co-precipitation route

Magnetic nanoparticles of nickel ferrite (NiFe₂O₄) have been synthesized by co-precipitation route using stable ferric and nickel salts with sodium hydroxide as the precipitating agent and oleic acid as the surfactant. X-ray diffraction (XRD) and transmission electron microscope (TEM) analyses confirmed the formation of single-phase nickel ferrite nanoparticles in the range 8-28 nm depending upon the annealing temperature of the samples during the synthesis. The size of the particles (d) was observed to be increasing linearly with annealing temperature of the sample while the coercivity with particle size goes through a maximum, peaking at ∼11 nm and then decreases for larger particles. Typical blocking effects were observed below ∼225 K for all the prepared samples. The superparamagnetic blocking temperature (T_B) was found to be increasing with increasing particle size that has been attributed to the increased effective anisotropy energy of the nanoparticles. The saturation moment of all the samples was found much below the bulk value of nickel ferrite that has been attributed to the disordered surface spins or dead/inert layer in these nanoparticles.     

Influence of initial pH on the particle size and fluorescence properties of the nano scale Eu(III) doped yttria

Europium doped ytrrium oxide (Eu:Y₂O₃) was synthesized by a chemical wet method in the presence of tween-80 and ?-caprolactam in pH range 4-10. It has been observed that the variation in surface area, pore size, and pore volume of the final product, was strongly dependent on the initial pH of the solution. The powder with a large surface area (∼230 m²/g) and low pore diameter (∼16 nm) was obtained when the powder was processed at pH ∼4. The crystallite sizes of the powders processed at pH ∼4 and 10, were found to be 35 and 198 nm, respectively. The structural, chemical and thermal studies of the powders were characterized by X-ray diffraction (XRD), Fourier transformed infrared spectrophotometer (FTIR), Carbon analyzer and Thermogravimetry (TGA). High resolution transmission electron microscopic (HRTEM) study of heat treated powders showed a polygonal morphology with particle size of 40 nm when powder was derived at pH ∼4. Observations of fluorescence suggested that the ⁵D₀→⁷F₂ transition within europium was found to be highly dependent on the initial pH.     

Functional Nanostructured Silica Powders Derived from Colloidal Suspensions by Sol Spraying

The preparation of silica powders derived from sols with a variety of primary particle sizes from 4 to 100 nm and the influences of preparation conditions such as drying temperature and initial concentration of precursor on the final powders morphology were investigated for the first time. The prepared silica powders have spherical morphology, and the final diameter (between 0.1 and 2 um) was controlled by changing the concentration of starting colloidal suspension. The preparation of silica based luminescent powders was investigated by adding europium ion as the dopant. The Eu-doped silica powders showed a visible-luminescence with wavelength of 613 nm, a red emission, under excitation of 394 nm light source. The effects of Eu-doping concentration, operation temperature and primary particle size of silica sols on the luminescence were also investigated.     

Synthesis and enhanced photocatalytic activity of NaNbO3 prepared by hydrothermal and polymerized complex methods

We prepared NaNbO₃ by several methods, namely solid-state reaction (SSR), hydrothermal (HT) and polymerized complex (PC) methods, and investigated the relationships between the photocatalytic activity and the particle size and morphology. The photocatalytic activity was evaluated by H₂ evolution from an aqueous methanol solution and pure water splitting in the presence of the Pt(0.5 wt%)/NaNbO₃ and RuO₂(1.25 wt%)/NaNbO₃, respectively. It is found that the sample prepared by PC with smallest particles exhibits the highest photocatalytic activity in both reactions. Moreover, the HT sample with the cubic and rectangular shape also shows the enhanced photocatalytic activity for H₂ evolution from an aqueous methanol solution in comparison with that of the sample prepared by SSR.     

The effect of functionalization on structure and electrical conductivity of multi-walled carbon nanotubes

Nanosized powders of Ti-Nb oxide core-shell nanocrystals with atomic ratios of Nb/Ti = 0.11, 0.25, and 0.38 have been prepared by two preparation routes. The first route was co-precipitation, followed by␣annealing, using NbCl₅ as a source of Nb. The second route was coating of pure TiO₂ nanocrystals by Nb-isopropoxide in liquid medium, followed by impregnation of the Nb into the nanoparticles by annealing. Both methods yielded anatase nanocrystals with a Nb-rich shell and a core, which had much lower Nb loadings. The anatase structure solid solution (with Nb incorporated) was stable under annealing up to 760°C. The particle size remained within the nanometric scale (<50 nm) under heat-treatment up to 760°C. It has been shown that the fabricated powders can be redispersed in aqueous media by simple ultrasound treatment, resulting in nanosized dispersions. Using a variety of analytical techniques, including depth profiling of single nanocrystallites by AES combined with sputtering by Ar ions, the mechanism of the core-shell structure creation was studied. It is proposed that the formation of the core-shell structure is governed by solubility limitations in the co-precipitation route and by solubility and diffusion limitations in the coating-incorporation route.