Synthesis of multi-walled carbon nanotubes using Co–Fe–Mo/Al2O3 catalytic powders in a fluidized bed reactor

The effects of the metal loading (30–70 wt.%), metal molar ratio (Co/Fe, 1–5) and mass ratio of citric acid to the catalyst (0–0.6) on the productivity and mean diameter of the multi-walled carbon nanotubes (MWCNTs) in a gas–solid fluidized bed reactor (with an inner diameter of 0.056 m and a height of 1.0 m) were determined. Liquefied petroleum gas (LPG) was used as the carbon source. X-ray diffraction (XRD) was used to characterize the catalysts synthesized using a combustion method. MWCNTs synthesized in the fluidized bed reactor were characterized by field emission scanning electron microscopy (FE-SEM) to observe their morphologies and measure their diameters. Productivity was increased by increasing both the metal loading and the mass ratio of citric acid to the catalyst. A high productivity, up to 2000%, was obtained. The catalyst transition metal particle grain size decreased in the range of 8–17 nm with an increasing citric acid mass ratio to the catalyst and the mean diameter of the MWCNTs decreased with increasing the metal molar ratio, however the correlation between the grain size in the catalyst and the mean diameter of MWCNTs remains unclear.     

Synthesis of nanocrystalline GaN from Ga2O3 nanoparticles derived from salt-assisted spray pyrolysis

Gallium nitride (GaN) nanoparticles were successfully produced from nano-sized gallium oxide (Ga₂O₃) particles under a flow of ammonia gas. The gallium oxide nanoparticles were prepared by salt-assisted spray pyrolysis (SASP). Highly crystalline Ga₂O₃ nanoparticles with an average diameter of approximately 10 nm were obtained at various temperatures when a flux salt (LiCl, 5 mol/l) was added to the precursor solution. The effects of the crystallinity of the Ga₂O₃ particles and nitridation time on transformation to GaN were characterized using X-ray diffraction and scanning/transmission electron microscopy. Highly crystalline GaN nanoparticles with a mean size of 23.4 nm and a geometric standard deviation of 1.68 nm were obtained when Ga₂O₃ nanoparticles with relatively low crystallinity were used as the starting material. The resulting GaN nanoparticles showed a photoluminescence peak at 364 nm under UV excitation at 254 nm.     

Sol–gel derived Cr(III) and Cu(II)/γ-Al2O3 doped solids: Effect of the dopant precursor nature on the structural,textural and morphological properties

Powders of xerogel γ-Al₂O₃ doped with various concentrations of Cr³⁺ and Cu²⁺ (M/M + Al molar fraction = 0.75–10%) were prepared via a sol–gel method. Cr³⁺ and Cu²⁺ precursors (acetylacetonate, nitrate or chloride) were added to 0.12 M 2-propanol solution of aluminum tri-sec-butoxide (ASB) and hydrolysis was performed using a H₂O/ASB molar ratio of 4.7. The effect of the dopant precursor on structural, textural and morphological properties was studied. Employing acac precursors resulted in unique properties after calcination at 500 °C including high surface areas, as high as 455 m²/g, homogeneous mesopores, 3–12 nm, and amorphous powders (5–10 nm particles in diameter). On the other hand, the acac precursor enhanced the resistance to sintering mainly at higher metal loads (10%) and elevated temperature (800 °C). Nevertheless, the solids issued from nitrate and chloride precursors exhibited lower surface areas at high metal loads, and lower resistance to sintering.     

Photoluminescence properties of Y3Al5O12:Eu nanocrystallites prepared by co-precipitation method using a mixed precipitator of NH4HCO3 and NH3·H2O

Europium-doped yttrium aluminum garnet (Y₃Al₅O₁₂:Eu, YAG:Eu) nanocrystallites were prepared by calcining the precursors obtained via a co-precipitation method using a mixed solution of NH₄HCO₃ and NH₃·H₂O as the precipitator. The results of XRD, FTIR and thermal analysis showed that phase-pure YAG:Eu without any other phases was obtained at 900 °C. TEM results indicated that the particle sizes are 50–100 nm. YAG:Eu nanocrystallites showed four emission bands ascribed to ⁵D₀ → ⁷F₁ transition (592 and 597 nm) and ⁵D₀ → ⁷F₂ transition (611 and 633 nm) of Eu³⁺, respectively. The intensity of the magnetic dipole transition (⁵D₀ → ⁷F₁) is stronger than that of the electric dipole transition (⁵D₀ → ⁷F₂). The influence of the precipitators with different molar ratios of NH₄HCO₃ to NH₃·H₂O on the thermal properties of the as-prepared precursors and luminescent properties of the resulting YAG:Eu nanocrystallites was also investigated.     

Fracture behaviour of α-Al2O3 ceramics reinforced with a mixture of single-wall and multi-wall carbon nanotubes

The extraordinary mechanical properties of single-wall carbon nanotubes (SWCNTs) and multi-wall carbon nanotubes (MWCNTs) have generated interest in incorporating them as toughening agents in ceramics. This work describes the fracture behaviour of an alumina (Al₂O₃) ceramic reinforced with a mixture of 0.05 wt% MWCNTs + 0.05 wt% SWCNTs. The CNT/Al₂O₃ nanocomposite was pressureless sintered in air using graphite powder as bed powder at 1520 °C for 1 h. The hardnesses and fracture toughnesses were lower than for pure Al₂O₃ and Al₂O₃ + 0.1 wt% SWCNTs and Al₂O₃ + 0.1 wt% MWCNTs. A predominantly transgranular fracture mode with a decrease in crack deflection and no pull-out was observed in the SWCNT + MWCNT–Al₂O₃ nanocomposite. MWCNTs had to the best reinforcing effect in Al₂O₃ nanocomposite.     

Polyvinylpyrrolidone (PVP)-assisted hydrothermal synthesis of luminescent YVO4:Eu3+ microspheres

Spherical YVO₄:Eu³⁺ microstructures were hydrothermally synthesized by the reaction of NH₄VO₃, Y₂O₃, and Eu₂O₃ at 180 °C for 24 h with the assistance of polyvinylpyrrolidone (PVP) as a surfactant. The resulting products were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence (PL) spectroscopy. The experimental results showed that ball-like YVO₄:Eu³⁺ microspheres with a diameter of about 4–5 μm, corresponding to the SEM observations, formed at 180 °C for 24 h using 0.2 g PVP with the molecular weight of 20,000 g mol^?1. The amount of PVP and the reaction time of hydrothermal processing were found to play a key role in the formation of YVO₄:Eu³⁺ microspheres. It has been observed that the relative luminescence intensities of the as-synthesized samples increased with increasing hydrothermal reaction times due mainly to the increase of crystallinity.     

Metal-organic deposition of biaxially textured CeO2–based buffer layers

Biaxially textured CeO₂-based oxide films with crack-free and smooth surface were prepared by metal-organic deposition (MOD) on Ni-W alloy tapes after annealing. In this study, addition of B₂O₃-based precursors to precursor solution and their effects on crystallinity and surface roughness of the CeO₂-based oxide films were investigated. As the amount of added B₂O₃-based precursors increased, the relative intensity of CeO₂ (200) peak was monotonously increased and much smoother surface was obtained. Microcracks in CeO₂ films were successfully suppressed by substituting gadolinium for part of cerium in the CeO₂ films. In addition to this, a biaxially textured Ce_0.75Gd_0.25O₂-4.5% B₂O₃ film (Δθ = 4.8°, Δ? = 7.4°) with smooth surface (R_q = 2.7 nm) was successfully grown on the Ni-W tape after annealing at 900 °C.     

Improvement of dry float–sink separation of smaller sized spheres by reducing the fluidized bed height

In this study, the influence of the fluidized bed height on the float–sink of different sized spheres in a gas–solid fluidized bed was investigated. Fluidized beds with heights h = 200, 150, 100 and 50 mm were prepared using a cylindrical column of inner diameter = 290 mm and a mixture of zircon sand and iron powder as the fluidized medium. Float–sink experiments were carried out using density adjusted spheres of diameter D_sp = 40, 30, 20 and 10 mm. It was found that the float–sink performance at D_sp ?20 mm is not affected by the height of the bed, and the sharpness of separation (the density range where spheres neither float nor sink completely) is less than or equal to 200 kg/m³. In the case of D_sp = 10 mm, the sharpness of separation is a larger value (1100 kg/m³ at h = 200 mm), whereas it decreases with decreasing h and is 400 kg/m³ at h = 50 mm. The fluctuation of the surface height of the fluidized bed was visually recorded. The fluctuation is reduced by reducing h. The fluctuation vs. h correlates with the sharpness of separation at D_sp = 10 mm vs. h. These results indicate that the dry float–sink separation of smaller sized spheres is improved as the fluctuation of fluidized bed surface is decreased by reducing the fluidized bed height.     

Controllable synthesis of multi-layer graphene flakes and multi-wall carbon nanotubes from pyrolyzing biodegradable poly(butylene succinate) composites

This work reports a simple method to synthesize multi-layer graphene flakes (MLGFs) and multi-wall carbon nanotubes (MWCNTs) from pyrolyzing biodegradable poly(butylene succinate) (―[OC(CH₂)₂COO(CH₂)₄O]_n―) composites. The obtained carbon nanomaterials were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). The SEM and TEM results indicated that the morphology of the carbon nanomaterials was significantly influenced by the catalyst precusors used. When MnO₂ was used as the catalyst precusor, MLGFs with the thickness between 1.4 and 4 nm were produced. However, when Ni₂O₃ was used, MWCNTs with the diameter of 18–28 nm were obtained. The XRD patterns demonstrated that MnO and Ni, in situ formed from MnO₂ and Ni₂O₃, were the active sites for the formation of MLGFs and MWCNTs respectively. On the basis of the results, a possible formation mechanism of MLGFs and MWCNTs was proposed.     

Magnetically-sensitive shape memory polyurethane composites crosslinked with multi-walled carbon nanotubes

Magnetically-sensitive polyurethane composites, which were crosslinked with multi-walled carbon nanotubes (MWCNTs) and were filled with Fe₃O₄ nanoparticles, were synthesized via in situ polymerization method. MWCNTs pretreated with nitric acid were used as crosslinking agents. Because of the crosslinking of MWCNTs with polyurethane prepolymer, the properties of the composites with a high content of Fe₃O₄ nanoparticles, especially the mechanical properties, were significantly improved. The composites showed excellent shape memory properties in both 45 °C hot water and an alternating magnetic field (f = 45 kHz, H = 29.7 kA m⁻¹). The shape recovery time was less than one minute and the shape recovery rate was over 95% in the alternating magnetic field.     

EPR and optical absorption studies of Cr3+ doped lithium potassium sulphate single crystals

X-band electron paramagnetic resonance (EPR) studies of Cr³⁺ doped lithium potassium sulphate single crystals have been done at room temperature. The Cr³⁺ crystal field and spin Hamiltonian parameters have been evaluated by employing resonance line positions observed in the EPR spectra for different orientations of external magnetic field. The evaluated g, D and E values are: g_x = 2.0763 ± 0.0002, g_y = 1.9878 ± 0.0002, g_z = 1.8685 ± 0.0002 and D = 549 ± 2 × 10^?4 cm^?1, E = 183 ± 2 × 10^?4 cm^?1. Using EPR data the site symmetry of Cr³⁺ ion in the crystal is discussed. Cr³⁺ ion enters the lattice substitutionally replacing K⁺ site. The optical absorption study of the single crystal is also done in 195–925 nm wavelength range at room temperature. By correlating optical and EPR data the nature of bonding in the crystal is discussed. The calculated values of Racah parameters (B and C), crystal field parameter (D_q) and nephelauxetic parameters (h and k) are obtained as: B = 697, C = 3247, D_q = 2050 cm^?1, h = 1.146 and k = 0.21.     

Effects of crystallinity and silica content on the hydration kinetics of 12CaO · 7Al2O3

The effects of 12CaO₇ · Al₂O₃ crystallinity on the kinetics of hydration reaction were studied by measuring the heat liberated using a conduction calorimeter. The crystallinity of the sample was modified by changing the cooling rate of the sample after synthesis reaction. In addition, the effects of silica addition to 12CaO₇ · Al₂O₃ glass on kinetics were also investigated. The results indicated that the glass underwent a faster initial kinetic hydration reaction compared with that of crystalline calcium aluminate. The addition of silica, on the other hand, decreased the reaction rates. The results are discussed in terms of the solvation rate of the calcium aluminate phases and the precipitation of the hydrate phases.     

A highly-sensitive l-lactate biosensor based on sol-gel film combined with multi-walled carbon nanotubes (MWCNTs) modified electrode

A new type of amperometric l-lactate biosensor based on silica sol-gel and multi-walled carbon nanotubes (MWCNTs) organic–inorganic hybrid composite material was developed. The sol-gel film was used to immobilize l-lactate oxidase on the surface of glassy carbon electrode (GCE). MWCNTs were used to increase the current response and improve the performance of biosensor. The sol-gel film fabrication process parameters such as H₂O : TEOS and pH were optimized, Effects of some experimental variables such as applied potential, temperature, and pH on the current response of the biosensor were investigated. Analytical characteristics and dynamic parameters of the biosensors with and without MWCNTs in the hybrid film were compared, and the results showed that analytical performance of the biosensor could be improved greatly after introduction of the MWCNTs. Sensitivity, linear range, limit of detection (S / N = 3) were 2.097 μA mM^− 1, 0.3 to 1.5 mM, 0.8 × 10^− 3 mM for the biosensor without MWCNTs and 6.031 μA mM^− 1, 0.2 to 2.0 mM, 0.3 × 10^− 3 mM for the biosensor with MWCNTs, respectively. This method has been used to determine the l-lactate concentration in real human blood samples.     

Potentiometric urea biosensor based on multi-walled carbon nanotubes (MWCNTs)/silica composite material

A novel potentiometric urea biosensor has been fabricated with urease (Urs) immobilized multi-walled carbon nanotubes (MWCNTs) embedded in silica matrix deposited on the surface of indium tin oxide (ITO) coated glass plate. The enzyme Urs was covalently linked with the exposed free –COOH groups of functionalized MWCNTs (F-MWCNTs), which are subsequently incorporated within the silica matrix by sol–gel method. The Urs/MWCNTs/SiO₂/ITO composite modified electrode was characterized by Fourier transform infrared (FTIR) spectroscopy, thermal gravimetric analysis (TGA) and UV–visible spectroscopy. The morphologies and electrochemical performance of the modified Urs/MWCNTs/SiO₂/ITO electrode have been investigated by scanning electron microscopy (SEM) and potentiometric method, respectively. The synergistic effect of silica matrix, F-MWCNTs and biocompatibility of Urs/MWCNTs/SiO₂ made the biosensor to have the excellent electro catalytic activity and high stability. The resulting biosensor exhibits a good response performance to urea detection with a wide linear range from 2.18 × 10^? 5 to 1.07 × 10^? 3 M urea. The biosensor shows a short response time of 10–25 s and a high sensitivity of 23 mV/decade/cm².     

Amperometric choline biosensors based on multi-wall carbon nanotubes and layer-by-layer assembly of multilayer films composed of Poly(diallyldimethylammonium chloride) and choline oxidase

A layer-by-layer deposition technique combined with Multi-wall carbon nanotubes (MWCNTs) was employed for fabricating choline sensors. The terminals and side-walls were linked with oxygen-containing groups when MWCNTs were treated with concentrated acid mixtures. A film of MWCNTs was initially prepared on the platinum electrode surface. Based on the electrostatic interaction between positively charged polyallylamine (PAA) and negatively charged MWCNTs and poly(vinyl sulfate) (PVS), a polymer film of (PVS/PAA)₃ was alternately adsorbed on the modified electrode continuously to be used as a permselective layer. Then poly(diallyldimethylammonium) (PDDA) and choline oxidase(ChOx) multilayer films were assembled layer-by-layer on the pretreated electrode, so an amplified biosensor toward choline was constructed. The choline sensor showed a linear response range of 5 × 10^? 7 to 1 × 10^? 4 M with a detection limit of 2 × 10^? 7 M estimated at a signal-to-noise ratio of 3, and a sensitivity of 12.53 μA/mM with a response time of 7.6 s in the presence of MWCNTs. Moreover, it exhibited excellent reproducibility, long-term stability as well as good suppression of interference. This protocol could be used to immobilize other enzymes for biosensor fabrication.     

Fluorescence properties and relaxation processes of Tb3+ ions in ZnCl2-based glasses

60ZnCl₂–20KCl–20BaCl₂–xTbCl₃ glasses (x = 0.10, 0.25, 0.50, 0.75, 1.00, and 1.25) were prepared by melt-quenching method, and Tb³⁺ fluorescence properties were investigated under 355 nm excitation. Regardless of x values, the electrons that were relaxed from the ⁵D₃ to ⁵D₄ level of Tb³⁺ ions by the multiphonon relaxation, were repressed to 28% of all the excited electrons because the ZnCl₂-based glass had much lower phonon energy than oxide glasses. For 0 < x ≤ 0.34, the cross relaxation, (⁵D₃ → ⁵D₄) → (⁷F₀ ← ⁷F₆), was repressed, and consequently 72% and 28% of all the excited electrons were radiatively relaxed by the ⁵D₃ → ⁷F_J (J = 6, 5, 4, 3, and 2) and ⁵D₄ → ⁷F_J (J = 6, 5, 4, and 3) transitions, respectively. The lifetimes of the ⁵D₃ and ⁵D₄ initial levels were obtained to be 1.1 and 2.1 ms, respectively.     

Enhanced photoluminescence features of Eu3+-modified di-ureasil-zirconium oxocluster organic–inorganic hybrids

In this work, a series of transparent di-ureasil hybrids containing different amounts of methacrylic acid modified zirconium tetrapropoxide (ZrMcOH) nanoclusters (5–85 mol%) and incorporating EuCl₃ and [Eu(tta)₃(H₂O)₂] (tta = thenoyltrifluoroacetonate) complex were prepared. These hybrids are multi-wavelength emitters due to the convolution of the host intrinsic emission (electron–hole recombinations occurring in siliceous and urea cross-linkages) Eu³⁺ intra-4f⁶ transitions. The ZrMcOH incorporation deviates the maximum excitation wavelength of the hybrid host intrinsic emission from the UV (365 nm) to the blue (420 nm) and enhances the absolute emission quantum yield from 6.0 ± 0.6% to 9.0 ± 0.9%, and contributes to an increase in the ⁵D₀ lifetime values, quantum efficiency due to a decrease in the non-radiative transition probability and OH groups coordinated to the Eu³⁺ ions.     

Synthesis of indium-catalyzed Si nanowires by hot-wire chemical vapor deposition

Indium (In) catalyzed silicon nanowires (SiNWs) were synthesized by using hot-wire chemical vapor deposition (HWCVD) technique. Indium droplets were deposited on Si substrates by hot-wire evaporation of In wire, which was immediately followed by the growth of SiNWs from the droplets. Three sets of samples were prepared by varying the length of In wires, l, as 3, 1 and 0.5 mm. The sizes of In catalyst droplets decreased from 271.4 ± 66.8 to 67.4 ± 16.6 nm when the l was reduced from 3 to 0.5 mm. Larger size of In droplets (271.4 ± 66.8 nm) was found to induce the growth of worm-like NWs. The decrease in size of In catalyst droplets induced the formation of aligned and tapered NWs with smaller tips. The smallest value of tapering parameter, T_p of 40.5 nm/μm is correlated to the SiNWs induced by the smallest size of In droplets (67.4 ± 16.6 nm). The as-grown SiNWs showed high purity and good crystalline structure.     

Preparation and characterization of LTA-type zeolite framework dispersed ruthenium nanoparticles and their catalytic application in the hydrolytic dehydrogenation of ammonia–borane for efficient hydrogen generation

The safe and efficient hydrogen storage and production are major obstacles to use hydrogen as an energy carrier. Therefore, significant efforts have been focused on the development of new materials for the chemical hydrogen storage and production. Of particular importance, ammonia–borane (NH₃BH₃) is emerging as one of the most promising solid hydrogen carrier due to its high gravimetric hydrogen storage capacity (19.6 wt.%) and low molecular weight (30.8 g/mol). ammonia–borane can release hydrogen gas upon catalytic hydrolysis under mild conditions. Herein, the discovery of a new catalytic material, ruthenium nanoparticles stabilized by ZK-4 zeolite framework, for this important reaction has been reported. This new catalyst system was prepared by borohydride reduction of ruthenium(III)-exchanged ZK-4 zeolite in water at room temperature. The characterization of the resulting material by advanced analytical tools shows the formation of ZK-4 zeolite dispersed ruthenium nanoparticles (2.9 ± 0.9 nm). The catalytic performance of the resulting supported ruthenium nanoparticles depending on activity, lifetime and reusability was demonstrated in the hydrolytic dehydrogenation of ammonia–borane. They were found to be highly active (initial TOF = 5410 h^?1), long-lived (TTO = 36,700) and reusable catalyst (retaining of >85% of initial activity in the 5th reuse) in this important catalytic reaction at room temperature under air.     

Effect of different solvents in the synthesis of LaCoO3 nanopowders prepared by the co-precipitation method

This paper describes the obtention of LaCoO₃ nanopowders by the co-precipitate method with ammonium hydroxide from solvent such as water, ethyl alcohol and ethylene glycol. The crystalline structure and average particle size are dependent of type-solvent. The XRD patterns indicated that the LaCoO₃ nanopowders prepared with water and ethyl alcohol exhibit a pure perovskite-type LaCoO₃ in the rhombohedra structure. The average diameter of the particles prepared with ethyl alcohol and water are 27 ± 4.49 nm and 64.4 ± 12.92 nm respectively. High resolution transmission electron microcopy revealed an oriented attachment mechanism for the growth of aggregated LaCoO₃ nanocrystals. Room temperature magnetization results of the heat treated LaCoO₃ nanopowders exhibited a paramagnetic behavior. The average particle size and formation temperature of LaCoO₃ obtained in this study is comparatively lower than those reported in the literature.