New strategy to obtain high surface area anatase nanotube/AuNP photocatalyst.

Anatase nanotubes with high surface area (ca. 350 m2 g-1), containing gold nanoparticles, were successfully obtained from trititanate nanotubes, prepared by a template-free hydrothermal method, and calcined at 450 °C. The high surface area and tubular morphology were attained due to the presence of ionic silsesquioxane, which acts as anti-sintering agent for titania during calcination process, by forming a thin silica coating between anatase nanotubes. Additionally, the ionic silsesquioxane also acts as stabilizing and adhesion agent for gold nanoparticles on the surface of anatase nanotubes. The influence of the ionic silsesquioxane on the morphological and textural properties of anatase nanotubes was studied in three different moments during the synthesis: before, after and before/after nanotubes were rolled up. The photocatalytic activity of the nanotube samples was evaluated by hydrogen generation showing remarkable enhancement in hydrogen production and stability of catalyst when compare with the bare anatase sample and commercial P-25.

Silver bonded to silica gel applied to the separation of polycyclic aromatic sulfur heterocycles in heavy gas oil.

Silica gel containing silver ions was prepared and characterized. Silica was organofunctionalized with 3-mercaptopropyl group by using grafting reaction followed by silver ions adsorption (silver covalently bonded to mercaptopropyl silca gel, Ag-MPSG). The organofunctionalization and silver coordination were observed by transmission infrared spectroscopy and elemental analyses (CHN and EDS). The textural characteristics were studied by N2 adsorption-desorption isotherms. Additionally, optical properties were studied by diffuse reflectance spectroscopy. The Ag-MPSG material was employed as stationary phase for the first time for fractionation of a heavy gas oil sample resulting in a fraction that is richer in polycyclic aromatic sulfur heterocycles (PASH). The fractions were analyzed by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometric detector and Ag-MPSG material provided similar fractionation performance when compared to conventional material [palladium covalently bonded to mercaptopropyl silca gel, Pd(II)-MPSG] usually employed for the same purpose and as the cost of silver is less than the one of palladium, the cost of the fractionation phase was reduced.

Effects of the large distribution of CdS quantum dot sizes on the charge transfer interactions into TiO2 nanotubes for photocatalytic hydrogen generation.

Hydrogen fuels generated by water splitting using a photocatalyst and solar irradiation are currently gaining the strength to diversify the world energy matrix in a green way. CdS quantum dots have revealed a hydrogen generation improvement when added to TiO2 materials under visible-light irradiation. In the present paper, we investigated the performance of TiO2 nanotubes coupled with CdS quantum dots, by a molecular bifunctional linker, on photocatalytic hydrogen generation. TiO2 nanotubes were obtained by anodization of Ti foil, followed by annealing to crystallize the nanotubes into the anatase phase. Afterwards, the samples were sensitized with CdS quantum dots via an in situ hydrothermal route using 3-mercaptopropionic acid as the capping agent. This sensitization technique permits high loading and uniform distribution of CdS quantum dots onto TiO2 nanotubes. The XPS depth profile showed that CdS concentration remains almost unchanged (homogeneous), while the concentration relative to the sulfate anion decreases by more than 80% with respect to the initial value after ∼100 nm in depth. The presence of sulfate anions is due to the oxidation of sulfide and occurs in greater proportion in the material surface. This protection for air oxidation inside the nanotubular matrix seemingly protected the CdS for photocorrosion in sacrificial solution leading to good stability properties proved by long duration, stable photocurrent measurements. The effect of the size and the distribution of sizes of CdS quantum dots attached to TiO2 nanotubes on the photocatalytic hydrogen generation were investigated. The experimental results showed three different behaviors when the reaction time of CdS synthesis was increased in the sensitized samples, i.e. similar, deactivation and activation effects on the hydrogen production with regard to TiO2 nanotubes. The deactivation effect was related to two populations of sizes of CdS, where the population with a shorter band gap acts as a trap for the electrons photogenerated by the population with a larger band gap. Electron transfer from CdS quantum dots to TiO2 semiconductor nanotubes was proven by the results of UPS measurements combined with optical band gap measurements. This property facilitates an improvement of the visible-light hydrogen evolution rate from zero, for TiO2 nanotubes, to approximately 0.3 µmol cm(-2) h(-1) for TiO2 nanotubes sensitized with CdS quantum dots.

Influence of Different Defects in Vertically Aligned Carbon Nanotubes on TiO2 Nanoparticle Formation through Atomic Layer Deposition.

The chemical inertness of carbon nanotubes (CNT) requires some degree of "defect engineering" for controlled deposition of metal oxides through atomic layer deposition (ALD). The type, quantity, and distribution of such defects rules the deposition rate and defines the growth behavior. In this work, we employed ALD to grow titanium oxide (TiO2) on vertically aligned carbon nanotubes (VACNT). The effects of nitrogen doping and oxygen plasma pretreatment of the CNT on the morphology and total amount of TiO2 were systematically studied using transmission electron microscopy, Raman spectroscopy, and thermogravimetric analysis. The induced chemical changes for each functionalization route were identified by X-ray photoelectron and Raman spectroscopies. The TiO2 mass fraction deposited with the same number of cycles for the pristine CNT, nitrogen-doped CNT, and plasma-treated CNT were 8, 47, and 80%, respectively. We demonstrate that TiO2 nucleation is dependent mainly on surface incorporation of heteroatoms and their distribution rather than structural defects that govern the growth behavior. Therefore, selecting the best way to functionalize CNT will allow us to tailor TiO2 distribution and hence fabricate complex heterostructures.

Structural, optical and photoelectrochemical characterizations of monoclinic Ta3N5 thin films.

Monoclinic Ta3N5 thin films were synthesized by thermal nitridation of amorphous Ta2O5 films directly sputtered by radio frequency magnetron sputtering. The samples were studied by high resolution transmission electron microscopy, X-ray photoelectron spectroscopy, UV-Vis-NIR spectrophotometry, rietveld refinements, spectroscopic ellipsometry and electrochemical techniques. The surface composition of Ta3N5 thin film was found to be different than the underlying film, affecting the optical properties of the material. Rietveld refinement has confirmed that the nitridation process results in Schottky and oxygen substitutional defects within the crystalline structure of monoclinic Ta3N5 thin film. The optical constants of the film were obtained by spectroscopic ellipsometry within a spectral range of 4.60-0.54 eV, i.e. 270-2300 nm. The suitable parameterization was found to consist of three Tauc-Lorentz and one Lorentz oscillators. The conduction band, valence band and the flat band positions were determined by photoelectrochemical techniques, presenting a strong dependence on pH of the eletrolyte. Improved photocurrent was obtained in alkaline conditions and attributed to the shorter depletion region width measured by Mott-Schottky and the lower recombination life time measured by open circuit potential decay analyses.

Glass window coatings for sunlight heat reflection and co-utilization.

Buildings that simultaneously provide natural illumination and thermal comfort for all seasons have met with increasing demand as conventional resource limitations are realized. In this context, organic and metal-dielectric coatings are tested, and a simple, coated double-glazed window with solar blinds is conceived that includes passive infrared (IR) reflection, active illumination control, and integration to the building envelope. As a result, a proper spectrally selective coating is applied to produce a low-emissivity solar window with climate-adaptive co-utilization of the reflected IR.

Simple modeling of plasmon resonances in Ag/SiO2 nanocomposite monolayers.

Normal incidence transmittance and reflectance spectra of sputtered nanocomposite monolayer films of Ag in SiO2, buried and unburied, showed significant redshifted plasmon resonances from 410 to 455 nm, which could be well interpreted with a simple model that starts from the Maxwell Garnett theory and the Kreibig extension of the Drude-Lorentz equation, but with a further extension related to the dipolar interaction between the metal particles distributed on a surface.

Spectral polarimetry technique as a complementary tool to ellipsometry of dielectric films.

Ellipsometry is a highly sensitive optical technique for coating characterization but usually presents multiple solutions in many cases. To prevent these, a method with addition of a spectral polarimetric technique is proposed. An initial film dispersion curve, independently of its physical thickness, is then provided using the same setup as spectral ellipsometry and at the same sample position, which later is used for thickness determination and dispersion refinement with increase of reliability of results. Characterization of thin TiO2 films with one and two ellipsometric solutions is shown to corroborate the validity of the proposed method.

Structural control of gold nanoparticles self-assemblies by layer-by-layer process.

This work presents a novel way to introduce gold nanoparticles (Au NPs) in a multilayer polymer produced by the layer-by-layer (LbL) assembling technique. The technique chosen shows that, depending on the pH used, different morphological structures can be obtained from monolayer or bilayer Au NPs. The MEIS and RBS techniques allowed for the modelling of the interface polymer-NPs, as well as the understanding of the interaction of LbL system, when adjusting the pH in weak polyelectrolytes. The process reveals that the optical properties of multilayer systems could be fine-tuned by controlling the addition of metallic nanoparticles, which could also modify specific polarization responses.

Solid immersion lens at the aplanatic condition for enhancing the spectral bandwidth of a waveguide grating coupler.

We report a technique to substantially boost the spectral bandwidth of a conventional waveguide grating coupler by using a solid immersion cylindrical lens at the aplanatic condition to create a highly anamorphic beam and reach a much larger numerical aperture, thus enhancing the spectral bandwidth of a free-space propagating optical beam coupled into a single-mode planar integrated optical waveguide (IOW). Our experimental results show that the broadband IOW spectrometer thus created almost doubles (94% enhancement) the coupled spectral bandwidth of a conventional configuration. To exemplify the benefits made possible by the developed approach, we applied the technique to the broadband spectroscopic characterization of a protein submonolayer; our experimental data confirm the enhanced spectral bandwidth (around 380-nm) and illustrate the potentials of the developed technology. Besides the enhanced bandwidth, the broadband coupler of the single-mode IOW spectrometer described here is more robust and user-friendly than those previously reported in the literature and is expected to have an important impact on spectroscopic studies of surface-adsorbed molecular layers and surface phenomena.

Low-Loss Optical Waveguides for the Near Ultra-Violet and Visible Spectral Regions with Al(2)O(3) Thin Films from Atomic Layer Deposition.

In this work, we report low-loss single-mode integrated optical waveguides in the near ultra-violet and visible spectral regions with aluminum oxide (Al(2)O(3)) films using an atomic layer deposition (ALD) process. Alumina films were deposited on glass and fused silica substrates by the ALD process at substrate/chamber temperatures of 200 °C and 300 °C. Transmission spectra and waveguide measurements were performed in our alumina films with thicknesses in the range of 210 - 380 nm for the optical characterization. Those measurements allowed us to determine the optical constants (n(w) and k(w)), propagation loss, and thickness of the alumina films. The experimental results from the applied techniques show good agreement and demonstrate a low-loss optical waveguide. Our alumina thin-film waveguides is well transparent in the whole visible spectral region and also in an important region of the UV; the measured propagation loss is below 4 dB/cm down to a wavelength as short as 250 nm. The low propagation loss of these alumina guiding films, in particular in the near ultra-violet region which lacks materials with high optical performance, is extremely useful for several integrated optic applications.

Simple polarimetric approach to direct measurement of the near-surface refractive index in graded-index films.

In the standard M-line method for the characterization of graded-index film, an analytical curve is fitted to the waveguide mode measurements and extrapolated to provide the refractive index in the zero-depth limit. Here we review our polarimetric approach to a direct near-surface measurement, which complements the M-line method. Also, we present its new and more straightforward version, which is applicable to existing samples and does not require masking before ion exchange.