Catalytic synthesis of bamboo-like multiwall BN nanotubes via SHS-annealing process

Bamboo-like multiwall boron nitride (BN) nanotubes were synthesized via annealing porous precursor prepared by self-propagation high temperature synthesis (SHS) method. The as-synthesized BN nanotubes were characterized by the field emission scanning electron microscopy (FE-SEM), transmission electron microscope (TEM), high-resolution TEM (HRTEM), X-ray diffraction (XRD), Raman and Fourier transform infrared (FTIR) spectroscopy. These nanotubes have uniform diameters of about 60 nm and an average length of about 10 μm. Four growth models, including tip, base, based tip and base-tip growth models, are proposed based on the catalytic vapor-liquid-solid (VLS) growth mechanism for explaining the formation of the as-synthesized bamboo-like BN nanotubes. Chemical reactions and annealing mechanism are also discussed.     

Multi-walled BN nanotubes synthesized by carbon-free method

Pure multi-walled BN nanotubes were synthesized via a carbon-free chemical vapor deposition process using boron and gallium oxide mixture as reaction precursor. Transmission electron microscopy was used to investigate their structure, morphology and defects. The wall deformation, dependent on tube diameter, was observed and explained in terms of strain relaxation of bond rotation. Opposed to carbon nanotubes, bending of BN nanotubes typically results in fracture at their concave side. Ring defect-related mechanism was proposed to interpret the fracture. The ring defects also result in the formation of a nanocone with 300° disclination. The nanocones end up with BN nanotubes exhibiting the small innermost shell ∼0.4 nm in diameter.     

Synthesis and characterization of layered double hydroxides (LDH) intercalated with non-steroidal anti-inflammatory drugs (NSAID)

Layered double hydroxides (LDHs) with the hydrotalcite type structure and a Mg:Al ratio of two have been prepared, with salicylate or naproxen in the interlayer. Two synthetic routes have been used: reconstruction from a mildly calcined hydrotalcite-CO₃ precursor, and a coprecipitation method with chlorides of the metals. The solids have been characterized using several physicochemical techniques, i.e., powder X-ray diffraction, FTIR and ¹³C CP/MAS NMR spectroscopies and thermal analysis (thermogravimetric and differential thermal analyses). The gallery height determined is in all cases larger than the size of the drug, 11.5 Å for salicylate and 15.8 and 16.6 Å for naproxen, depending on the specific synthesis route followed. Experimental data suggest the anion molecules form a tilted bilayer, with the carboxylate groups pointing towards the brucite-like layers. The solids are stable up to 230 °C and their evolution from 350 °C upwards is very similar to that observed for a carbonate-containing hydrotalcite, forming mostly amorphous solids with a large specific surface area.     

Evolution of structural features and mechanical properties during the conversion of poly[(methylamino)borazine] fibers into boron nitride fibers

Poly[(methylamino)borazine] (PolyMAB) green fibers of a mean diameter of 15 μm have been pyrolyzed under ammonia up to 1000°C and heat treated under nitrogen up to 2000°C to prepare boron nitride (BN) fibers. During the polymer-to-ceramic conversion, the mechanical properties of the green fibers increase within the 25-400°C temperature range owing to the formation of a preceramic material and remain almost constant up to 1000°C. Both the crystallinity and the mechanical properties slightly increase within the 1000-1400°C range, in association with the consolidation of the fused-B₃N₃ basal planes. A rapid increase in tensile strength (σ^R) and elastic modulus (Young's modulus E) is observed in relation with crystallization of the BN phase for fibers treated between 1400°C and 1800°C. At 2000°C, “meso-hexagonal” BN fibers of 7.5 μm in diameter are finally obtained, displaying values of σ^R=1.480 GPa and E=365 GPa. The obtention of both high mechanical properties and fine diameter for the as-prepared BN fibers is a consequence of the stretching of the green fibers on a spool which is used during their conversion into ceramic.     

Simple synthesis of mesoporous boron nitride with strong cathodoluminescence emission

Mesoporous BN was prepared at 550 °C for 10 h or so via a simple reaction between NaBH₄ and CO(NH₂)₂. X-ray diffraction demonstrates the formation of t-BN with lattice constants a=2.46 and c=6.67 Å. High-resolution transmission electron microscopy displays a lot of porous films in the product, which possesses a high surface area of 219 m² g⁻¹ and a pore size primarily around 3.8 nm tested by nitrogen adsorption-desorption method. The mesoporous BN exhibits a strong luminescence emission around 3.41 eV in the cathodoluminescence spectra, a high stability in both morphology and structure, and good oxidation resistance up to 800 °C. The byproducts generated during the reaction are responsible for the formation of the mesoporous BN.     

High surface area V-Mo-N materials synthesized from amine intercalated foams

Nanocrystalline ternary V-Mo nitrides were prepared via nitridation of amine intercalated oxide foams or bulk ternary oxides. Specific surface areas were in the range between 40 and 198 m² g⁻¹ and strongly depended on the preparation method (foam or bulk oxide). Foamed precursors were favorable for vanadium rich materials, while for molybdenum rich samples bulk ternary oxides resulted in higher specific surface areas. The materials were characterized via nitrogen physisorption at 77 K, X-ray diffraction patterns, electron microscopy, and elemental analysis.     

Preparing nanometer scaled Tb-doped Y2O3 luminescent powders by the polyol method

Sub-micrometer Tb-doped Y₂O₃ luminescent powders were prepared from nitrate precursors using the polyol method. Just after precipitation, the powders consist of agglomerates with a spherical shape and a size ranging between 400 and 500 nm. Each agglomerate is composed of ultra-small crystallites (from 3 to 6 nm) of a bcc oxide phase whose luminescence presents original features in comparison with bulk materials. Powders were further calcinated at different temperatures and for annealing below 900 °C, highly crystalline samples with the classical green ⁵D₄→⁷F₅ luminescent transitions of Tb³⁺ ions are obtained. For optimized annealing temperatures, sintering between the agglomerates is avoided and a sub-micrometric powder with a narrow size distribution and a high luminescence is obtained.     

Nitridation under ammonia of high surface area vanadium aerogels

Vanadium pentoxide gels have been obtained from decavanadic acid prepared by ion exchange on a resin from ammonium metavanadate solution. The progressive removal of water by solvent exchange in supercritical conditions led to the formation of high surface area V₂O₅, 1.6H₂O aerogels. Heat treatment under ammonia has been performed on these aerogels in the 450-900 °C temperature range. The oxide precursors and oxynitrides have been characterized by XRD, SEM, TGA, BET. Nitridation leads to divided oxynitride powders in which the fibrous structure of the aerogel is maintained. The use of both very low heating rates and high surface area aerogel precursors allows a higher rate and a lower threshold of nitridation than those reported in previous works. By adjusting the nitridation temperature, it has been possible to prepare oxynitrides with various nitrogen enrichment and vanadium valency states. Whatever the V(O,N) composition, the oxidation of the oxynitrides in air starts between 250 and 300 °C. This determines their potential use as chemical gas sensors at a maximum working temperature of 250 °C.     

Pentacene precursors for solution-processed OFETs

15-Acetoxy- and 15-hydroxy-6,13-dihydro-6,13-ethanopentacenes sublimed over 300 °C and no pentacene was formed below the temperature. The precursors bearing chlorinated epithiomethano bridges suffered complicated decomposition to give oligomeric pentacene derivatives. The precursor bearing an epithio-oxomethano bridge underwent smooth and clean conversion to pentacene by heat or light. An organic field-effect transistor fabricated by the spin-coating method of the precursor followed by light irradiation at 120 °C showed a good FET performance of μ=2.5×10⁻² cm² V⁻¹ s⁻¹ and on/off ratio=3.8×10⁴.     

Mechanochemical-hydrothermal synthesis of calcium phosphate powders with coupled magnesium and carbonate substitution

Magnesium- and carbonate-substituted calcium phosphate powders (Mg-, CO₃-CaP) with various crystallinity levels were prepared at room temperature via a heterogeneous reaction between MgCO₃/Ca(OH)₂ powders and an (NH₄)₂HPO₄ solution using the mechanochemical-hydrothermal route. X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis were performed. It was determined that the powders containing both Mg²⁺ and CO₃²⁻ ions were incorporated uniformly into an amorphous calcium phosphate phase while in contrast, the as-prepared powder free of these dopants was crystalline phase-pure, stoichiometric hydroxyapatite. Dynamic light scattering revealed that the average particle size of the room temperature Mg-, CO₃-CaP powders was in the range of 482 nm-700 nm with a specific surface area between 53 and 91 m²/g. Scanning electron microscopy confirmed that the Mg-, CO₃-CaP powders consisted of agglomerates of equiaxed, ≈20-35 nm crystals.     

Synthesis of nanocrystalline REBO3 (RE=Y, Nd, Sm, Eu, Gd, Ho) and YBO3:Eu using a borohydride-based solution precursor route

A solution precursor route has been used to synthesize a series of nanocrystalline rare-earth borates. Amorphous precursor powders are precipitated during an aqueous reaction between RE³⁺ and NaBH₄, and the isolated powders can be annealed in air at 700 °C to form YBO₃, NdBO₃, SmBO₃, EuBO₃, GdBO₃, and HoBO₃. YBO₃:Eu formed using this strategy shows red-orange emission properties that are similar to high-quality nanocrystals prepared by other methods. The materials have been characterized by FTIR spectroscopy, powder XRD, SEM, DSC, UV-Vis fluorimetry, and TEM with EDS and element mapping.     

Fluorine-doped nanocrystalline SnO2 powders prepared via a single molecular precursor method as anode materials for Li-ion batteries

Fluorine-doped nanocrystalline tin dioxide materials (F:SnO₂) have been successfully prepared by the sol-gel process from a single molecular precursor followed by a thermal treatment at 450-650 °C. The resulting materials were characterized by FTIR spectroscopy, powder X-ray diffraction, nitrogen adsorption porosimetry (BET) and transmission electron microscopy (TEM). The mean particle size increased from 5 to 20 nm and the specific surface area decreased from 123 to 37 m²/g as the temperature of heat treatment was risen from 450 to 650 °C. Fluorine-doped nanocrystalline SnO₂ exhibited capacity of 560, 502, and 702 mA h/g with 48%, 50%, and 40% capacity retention after 25 cycles between 1.2 V and 50 mV at the rate of 25 mA/g, respectively. In comparison, commercial SnO₂ showed an initial capacity of 388 mA h/g, with only 23% capacity retention after 25 cycles.     

Hollow boron nitride (BN) nanocages and BN-nanocage-encapsulated nanocrystals

Hollow boron nitride (BN) nanocages (nanospheres, image on the left) and BN-nanocage-encapsulated GaN nanocrystals (right) have been synthesized by using a homemade B-N-O precursors. The as-prepared BN hollow nanocages have typically spherical morphologies with diameters ranging from 30 to 200 nm. The nanocages have crystalline structures. Peanutlike nanocages with double walls have also been observed; their internal space is divided into seperated compartments by the internal walls. The method is extended to sheathe nanocrystals with BN nanocages; BN-shell/GaN-core nanostructures have been successfully fabriacted. The method may be generally applicable to the fabrication BN-sheathed nanocrystals.     

Synthesis of highly crystalline rhombohedral BN triangular nanoplates via a convenient solid state reaction

Highly crystalline rhombohedral boron nitride (r-BN) with regular triangular shapes were synthesized on a large scale in a stainless steel autoclave using B₂O₃ and NaNH₂ as reactants at 600 °C for 6 h. The as-prepared BN triangular nanoplates have an average edge length of 400 nm and the thickness of about 60 nm. The photoluminescence measurements reveal that the r-BN products show strong yellow-green emission. The as-prepared r-BN has potential optical and optoelectronic applications in high temperature devices due to its excellent thermal stability and anti-oxidation properties.     

Effects of hydrothermal post-treatment on microstructures and morphology of titanate nanoribbons

Titanate nanoribbons were prepared via a hydrothermal treatment of rutile-type TiO₂ powders in a 10 M NaOH solution at 200 °C for 48 h. The as-prepared titanate nanoribbons were then hydrothermally post-treated at 150 °C for 12-36 h. The titanate nanoribbons before and after hydrothermal post-treatment were characterized with FESEM, XRD, TEM, UV-VIS and nitrogen adsorption-desorption isotherms. The results showed that the hydrothermal post-treatment not only promoted the phase transformation from titanate to anatase TiO₂, but also was beneficial to the removal of Na⁺ ions remained in the titanate nanoribbons. After hydrothermal post-treatment, the TiO₂ samples retained the one-dimensional structure feature of the titanate nanoribbons and showed an obvious increase in the specific surface area and the pore volume.     

Efficient palladium catalysts for the amination of aryl chlorides: a comparative study on the use of phosphium salts as precursors to bulky, electron-rich phosphines

Alkyl-di-(1-adamantyl)phosphonium salts are practical ligand precursors for the palladium-catalyzed amination of aryl chlorides. In the presence of typically 0.5 mol% Pd(OAc)₂ and 1 mol% of ligand precursor a variety of activated and deactivated aryl chlorides can be aminated in good to excellent yield (73-99%). Applying optimized conditions catalyst turnover numbers up to 10,000 have been achieved.     

Amperometric sensing of norepinephrine at picomolar concentrations using screen printed,high surface area mesoporous carbon

Norepinephrine (NE) is detected amperometrically using the enzyme Phenylethanolamine N-methyl transferase and cofactor S-(5′-Adenosyl)-l-methionine chloride dihydrochloride with disposable screen printed mesoporous carbon electrodes. The role of internal surface area and pore size of the mesoporous carbon is systematically examined using soft-templated, mesoporous silica–carbon powders with highly microporous walls obtained from etching of the silica to produce powders with surface areas ranging from 671–2339 m² g⁻¹. As the surface area increases, the sensitivity of the biosensor at very low NE concentrations (0–500 pg mL⁻¹) in phosphate buffered saline (PBS) increases just as the current signal increases with respect to the NE concentration of 81–1581 μA mL ng⁻¹ cm⁻² for the mesoporous carbons. The best performing electrode provides similar sensitivity in whole rabbit blood in comparison to PBS despite no membrane layer to filter the non-desired reactants; the small (<5 nm) pore size and large internal surface area acts to minimize non-specific events that decrease sensitivity.     

Acid and redox properties of mixed oxides prepared by calcination of chromate-containing layered double hydroxides

Layered double hydroxides (LDHs) with Mg and Al in the layers and carbonate, nitrate or chloride in the interlayer, or with Zn and Al in the layers and chloride in the interlayer, have been prepared by coprecipitation, and have been used as precursors to prepare chromate-containing LDHs. All these systems, as well as those obtained upon their calcination up to 800 °C, have been characterised by powder X-ray diffraction, FT-IR and vis-UV spectroscopies, temperature-programmed reduction (TPR), nitrogen adsorption at −196 °C for surface texture and porosity assessment, and FT-IR monitoring of pyridine adsorption for surface acidity determination. The results obtained show that the crystallinity of the chromate-containing LDH depends on the precursor used. The layered structure of the Mg, Al systems is stabilised up to 400 °C upon incorporation of chromate; however, the Zn,Al-chromate samples collapse between 200 and 300 °C, with simultaneous formation of ZnO. Calcination of the samples above 400 °C gives rise to a reduction of Cr(VI) to Cr(III), as concluded from vis-UV spectroscopic studies. The TPR profiles show that chromate in ZnAl hydrotalcite is more easily reduced than that incorporated in the magnesium ones. Moderately strong surface Lewis acid sites exist in all samples calcined below 500 °C.     

Development of a membrane reactor for decomposing hydrogen sulfide into hydrogen using a high-performance amorphous silica membrane

We have successfully developed a membrane reactor for decomposing hydrogen sulfide into hydrogen using an amorphous silica membrane for the first time. The membrane was prepared by the CVD method with tetramethoxysilane and oxygen, and showed excellent hydrogen permeance at 873 K of the order of 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ and high hydrogen/nitrogen permselectivity of 10⁴. The membrane reactor constructed with our membrane and a commercially available catalyst decomposed hydrogen sulfide into hydrogen with higher conversion than the equilibrium conversion. This conversion enhancement was because of the selective extraction of hydrogen from the reaction side to the permeate side by the silica membrane.     

Nonenzymatic glucose sensor based on CuO microfibers composed of CuO nanoparticles

Fluorine tin oxide (FTO) electrode modified by copper oxide microfibers (CuO-MFs) composed of numerous interconnected CuO nanoparticles (CuO-NPs) for nonenzymatic glucose sensor was prepared by electrospinning precursor containing high percentage content of copper nitrate with subsequent calcination. The results of scanning electron microscope (SEM) showed the size of CuO particles composing CuO-MFs depended on the percentage content of copper nitrate in precursor solution. With increasing the percentage content of copper nitrate, the interconnected CuO-NPs would gradually replace the large-size CuO particles to accumulate the CuO-MFs, which have the potential to provide larger surface area and more reaction sites for electrocatalytic activity toward glucose. As a glucose sensor, the CuO-MFs modified FTO electrode prepared by 40 wt.% of copper nitrate exhibited a high sensitivity of 2321 μA mM⁻¹ cm⁻² with a low detection limit of 2.2 nM (signal/noise ratio (S/N) = 3). Additionally, the application of the CuO-MFs modified FTO electrode as a glucose sensor for biological samples was demonstrated with satisfactory results.