Layer-by-layer assembly of TiO2 nanowire/carbon nanotube films and characterization of their photocatalytic activity.

We report on the layer-by-layer (LbL) formation of TiO(2)-MWNT-TiO(2) coatings on quartz with either trititanate derived TiO(2) nanowires or Degussa P25 as the photocatalytically active material. The optimized deposition sequence is discussed in detail and the morphology of the prepared coatings is analyzed by SEM and XRD. The heterogeneous photocatalytic performance of the coatings was tested in the methyl orange oxidation reaction. The apparent first order rate constant fell in the 0.01-0.20 h(-1) range over a 2.5 × 2.5 cm(2) film depending on the type and the thickness of the titanate coating. Building a multiwall carbon nanotube layer into the middle of the layer improved the photocatalytic activity for each material for all of the studied thicknesses. P25 based films performed 2-5 times better than TiO(2) nanowire films; however, the pores in the P25 based films were largely blocked because the isotropic P25 nanoparticles form closely packed layers by themselves and even more so with the comparably sized multiwall carbon nanotubes. Therefore, films derived from titanate nanowires appear to be more suitable for use as multifunctional, photocatalytically active filtration media.

Subacute intratracheal exposure of rats to manganese nanoparticles: behavioral, electrophysiological, and general toxicological effects.

The toxicity of manganese-containing airborne particles is an important occupational and environmental problem. In this work, adult male Wistar rats were treated with a nanosuspension of MnO(2) of approximately 23 nm nominal particle diameter, instilled into the trachea for 3, 6, and 9 wk in doses of 2.63 and 5.26 mg Mn/kg. The animals' body weight was checked weekly. At the end of treatment, the rats' spontaneous motility was tested in an open field box. Then, spontaneous and stimulus-evoked cortical activity and action potential of the tail nerve were recorded in urethane anesthesia. The rats were finally dissected, organs weights were measured, and the presence of excess Mn in lung and brain samples was determined using scanning electron microscopy with energy-dispersive x-ray spectroscopy. While control rats had normal weight gain, the body weights of the treated rats ceased to grow from wk 6 on. The relative weight of the lungs increased in the treated rats, and that of the liver decreased, in a dose- and time-dependent manner; Mn was detected in their lung and brain samples. In the open field activity, the percentage of ambulation and rearing decreased while local activity and immobility increased. The latency of the evoked potentials was lengthened, and the conduction velocity of the tail nerve decreased. These results indicate that the Mn content of instilled nanoparticles had access from the airways to the brain, and the resulting damage could be investigated in animals using neuro-functional and general toxicological endpoints.

Morphology and N2 permeability of multi-wall carbon nanotube--Teflon membranes.

We prepared buckypapers with surface densities in the 1.13-5.66 mg x cm(-2) range by filtering multi-wall carbon nanotube (MWCNT) suspensions in acetyl-acetone (acac) and dimethylformamide (DMF) through 0.45 microm nylon filters. Filtration curves were evaluated using the Carman equation. The average resistance of the filter itself was found to be Rm = 3.79 x 10(10) m(-1) for acac and 8.49 x 10(10) m(-1) for DMF The specific resistance a of the filter cakes decreased with increasing film surface density from 16.1 x 10(12) m x kg(-1) (for the 1.13 mg x cm(-2) film from DMF) to 4.38 x 10(12) m x kg(-1) (for the 5.66 mg x cm(-2) film from DMF). The effective diffusivity of N2 at 298 K and a pressure difference of 10 mbar was also determined for all membranes and found to fall into the 1.14 x 10(-9)-3.74 x 10(-9) m2 x s(-1) range. Both the porosity and the tortuosity of buckypapers increased with their thickness. An approx. 5 microm thick Teflon (PTFE) coating was applied to the MWCNT membranes by pulsed laser deposition. The gas permeability of the MWCNT-PTFE membranes matches that of the uncoated nanotube films. This observation is an agreement with our SEM and AFM data on porous coating morphology.

Oriented crystal growth model explains the formation of titania nanotubes.

We discuss the formation mechanism of titania nanotubes synthesized by the hydrothermal method. On the basis of a comprehensive analysis of TEM, HRTEM, FT-Raman, and N(2) adsorption data, we point out some major shortcomings of the currently accepted trititanate sheet rollup mechanism. We suggest that a novel formation mechanism, oriented nanotube crystal growth from nanoloop seeds, can explain the experimental findings better than the ones proposed so far.

Low temperature CO oxidation over iron-containing MCM-41 catalysts.

Different MCM-41 samples containing framework iron were prepared and tested in CO oxidation showing unprecedented high activities after reduction in hydrogen above 773 K.

Binary solvent mixture adsorption as a characterisation tool to determine the hydrophilic/hydrophobic properties of multiwall carbon nanotubes.

A simple method is offered to quantitatively characterise the hydrophobic/hydrophilic properties of carbon nanotubes by measuring binary solvent mixture adsorption.

Synthesis and characterization of hyperbranched mesoporous silica SBA-15.

Branched mesoporous silica SBA-15 materials have been prepared in a simple process using non-ionic surfactant in acidic conditions in the presence of metal ions.

Metal Substitution in Keggin-Type Tridecameric Aluminum-Oxo-Hydroxy Clusters.

The species resulting from a typical preparation for metal-substituted hybrids of the Keggin tridecamer, Al13 or [AlO4Al12(OH)24(OH2)12]7+, were examined by performing 27Al NMR on the solutions during aging and by studying the precipitated sulfate salts via solid state 27Al NMR and powder X-ray diffraction (XRD). Aqueous mixtures (0.25 mol L-1) of AlCl3 and another metal ion (M), in a 12:1 mole ratio (Al:M), where M = Fe3+, Zn2+, Ga3+, In3+, Sn2+, La3+, and Bi3+, were subjected to forced hydrolysis by addition of NaOH (1.0 mol L-1) until OH/(Al + M) = 2.25, and the kinetics of Al13 formation and disappearance with aging at 80 °C was monitored by 27Al NMR spectroscopy. Al13 units polymerize on aging with an apparent rate constant (k) of 4.8(8) × 10-2 h-1 to form a species referred to as AlP2. Only the solutions containing Ga3+ and Sn2+ exhibited faster Al13 conversion rates. GaAl12 forms quickly at 80 °C (k = 0.54 h-1) and is more stable than AlP2. Sn2+ apparently promotes AlP2 formation (k = 0.38 h-1). XRD and solid state NMR reveal that only the Ga hybrid can be prepared by this method. No hybrid formation was evidenced using M = Mg2+, Fe3+, Co2+, Ni2+, Cu2+, Zn2+, In3+, La3+, or Ce3+ at 25 °C or M = Co2+ or La3+ under reflux conditions. Isostructural (cubic symmetry) single crystals were obtained for the sulfate salts of Al13 and GaAl12. Single-crystal XRD analysis of these two polyoxocations provides the first rigorous comparison between them and shows they have very similar structures. The main crystallographic data for Al13 and GaAl12 are as follows: Na[AlO4Al12(OH)24(H2O)12](SO4)4·10H2O, cubic, F4̄3m, a = 17.856(2) Å, Z = 4; Na[GaO4Al12(OH)24(H2O)12](SO4)4·10H2O, cubic, F4̄3m, a = 17.869(3) Å, Z = 4. Thus, the greater thermal stability of GaAl12 cannot be rationalized in terms of the overall geometric considerations, as suggested by others. Solid state NMR also shows the coordination symmetries of the outer 12 Al nuclei in both clusters to be similar.

Mesoporous silicates as nanoreactors for carbon nanotube production in the absence of transition metal catalysts.

Carbon nanotubes were produced from either a template or the polymer-filled pore systems of mesoporous silicates of various structures and dimensions by heat treatment in the absence of air. Successful synthesis was done when the template molecules contained little or no oxygen. For SBA-15 material, where the structure-directing molecule used for synthesis of mesoporous silicate was polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, no carbon nanostructures were formed. A peculiar carbon nanostructure was generated from the template for pore expanded MCM-41. To demonstrate carbon nanotube formation from polymer in the mesoporous silicates, the mesopores of MCM-41, MCM-48, and SBA-15 silicates were filled with divinyl-benzene polymer and then graphitized at 1300 K. The polymer was successfully transformed into carbon nanotubes for the MCM class silicate but not the SBA-15 silicate.

Three-dimensional carbon nanotube scaffolds as particulate filters and catalyst support membranes.

Three-dimensional carbon nanotube scaffolds created using micromachined Si/SiO2 templates are used as nanoparticulate filters and support membranes for gas-phase heterogeneous catalysis. The filtering efficiency of better than 99% is shown for the scaffolds in filtering submicrometer particles from air. In the hydrogenation of propene to propane reaction low activation energy of E(a) approximately 27.8 +/- 0.6 kJ x mol(-1), a considerably high turnover rate of approximately 1.1 molecules x Pd site(-1) x s(-1) and durable activity for the reaction are observed with Pd decorated membranes. It is demonstrated that appropriate engineering of macroscopic-ordered nanotube architectures can lead to multifunctional applications.