Preparation of Ru-loaded CdS/Al-HMS nanocomposites and production of hydrogen by photocatalytic degradation of formic acid

The composite of aluminum-substituted mesoporous silica (Al-HMS) molecular sieve coupled with CdS (CdS/Al-HMS) was prepared by template, ion exchange and sulfurization reactions. The result of low angle XRD patterns showed that the low content of 2.5 wt% CdS is incorporated inside Al-HMS channels. The results of diffuse reflectance UV-visible spectra and fluorescence emission spectra exhibited that the absorption edge and photoluminescence peak for CdS/Al-HMS are blue-shifted about 75 nm and 40 nm in comparison to bulk CdS, respectively. The activities of hydrogen production by photocatalytic degradation of formic acid were evaluated under visible light irradiation (λ ≥ 420 nm) and the CdS/Al-HMS loaded 0.07 wt% Ru showed the highest H₂ evolution at a rate of 3.7 mL h⁻¹ with an apparent quantum yield of 1.2% at 420 nm.     

High‐density guided growth of silicon nanowires in nanoporous alumina on Si(100) substrate: Estimation of activation energy

High‐density growth of silicon nanowires confined within a nanoporous alumina template is carried out. The growth rate is measured for several temperatures. An incubation time is observed and measured. The activation energy of this system is calculated and compared to that of growth on a free silicon surface. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electrical behaviour of catalytic nanostructured CeO2/CuOx composites under air-methane gas impulses

Nanostructured composites based on copper oxide and cerium dioxide phases [CuO-CeO₂] were elaborated from sol-gel route, with weight fractions of CuO phase ranging between 0 and 0.4. They are interesting potential catalysts allowing conversion of CH₄ and CO into CO₂ and H₂O and might be used in miniaturized gas sensors. An electrical study of this nanostructured system was carried out to determine catalytic behaviours under air-methane impulses at 350 °C. The electrical analysis was based on a specific homemade electronic device. Time dependent interactions between gas pulses and solid catalyst (CuO/CeO₂) were analyzed from a frequency modification of the electronic device. Kinetic parameters were determined from a model describing adsorption and desorption of gases adapted to short interaction time between gas and solid. These time dependent electrical behaviours were then correlated with infrared spectroscopy analyses allowing time dependent analysis of methane conversion into CO₂ gas, for long interaction time between gas and solid.     

Desorption of metal atoms with laser light of different polarization

Laser-induced desorption of metal atoms from the surface of small metal particles has been investigated as a function of the shape of the particles and the polarization of the incident laser light. The particles were supported on LiF, quartz or sapphire substrates. In a first set of experiments, the shape of the particles was determined by recording optical transmission spectra with s- and p-polarized light incident under an angle of typically 40° with respect to the surface normal. The metal particles turn out to be oblate, the ratio of the axes perpendicular and parallel to the substrate surface being on the order of 0.5. This ratio decreases with increasing particle size. Also, the particles change shape if the temperature is raised. In further experiments, s- and p-polarized light has been used to stimulate desorption of atoms via surface plasmon excitation. It is found that the desorption rate markedly depends on the polarization of the light. This is explained by excitation of the collective electron oscillation along different axes of the non-spherical particles.     

Synthesis and characterization of ZnO-Ag core-shell nanocomposites with uniform thin silver layers

This paper presents an investigation on the synthesis and characterization of ZnO-Ag core-shell nanocomposites. ZnO nanorods were employed as core material for Ag seeds, and subsequent nucleation and growth of reduced Ag by formaldehyde formed the ZnO-Ag core-shell nanocomposites. The ZnO-Ag nanocomposites were annealed at different temperature to improve the crystallinity and binding strength of Ag nanoparticles. The morphology, microstructure and optical properties of the ZnO-Ag core-shell nanocomposites were characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, ultraviolet-visible (UV-vis) absorption and photoluminescence measurement. It was demonstrated that very small face-center-cubic Ag nanoparticles were coated on the surface of ZnO nanorods. The ultraviolet absorption and surface plasmon absorption band of ZnO-Ag core-shell nanocomposites exhibited some redshifts relative to pure ZnO nanorods and monometallic Ag nanoparticles. The coating of Ag nanocrystals onto the ZnO nanorods completely quenched the photoluminescence. These observations reflected the strong interfacial interaction between ZnO nanorods and Ag nanoparticles. The effect of Ag coating thickness on the morphology and optical properties of ZnO-Ag core-shell nanocomposites was also investigated. Moreover, the growth mechanism of ZnO-Ag core-shell nanocomposites was also proposed and discussed in detail.     

Growth of Pure Zinc Blende GaAs Nanowires: Effect of Size and Density of Au Nanoparticles

Pure zinc blende GaAs nanowires were grown by metal organic chemical vapor deposition on GaAs（111）B substrates via Au catalyzed vapor-liquid-solid mechanism. The diameter, size distribution, and density of Au particles can be changed by varying the Au film thickness. We find that the grown nanowires are of rod-like shapes and pure zinc blende structure; moreover, the growth rate depends on the density of Au particles and it is independent of its diameters. It can be concluded that the nanowire was grown with main contributions from the direct impingement of vapor species onto the Au-Ga droplets and contributions from adatom diffusion can be negligible. The results indicate that the droplet acts as a catalyst rather than an adatom collector.     

Plasma-electrolytic formation, composition and catalytic activity of manganese oxide containing structures on titanium

In the present work, we report the data about formation of TiO₂-rutile or TiO₂ and Mn₂O₃, Mn₃O₄ containing oxide structures on titanium in aqueous electrolytes by means of plasma-electrolytic deposition. The layers formed are characterized by X-ray diffraction, electron probe microanalysis and scanning electron microscopy methods. The PEO coatings on titanium formed in sodium tetraborate solution contain the TiO₂ stabile rutile modification that is important when utilizing such a structure as a catalyst carrier. Manganese acetate adding into the electrolyte leads to formation of layers that contain Mn₂O₃, Mn₃O₄ and TiO₂-rutile in outer region. The manganese content in the surface layer depends on the formation conditions as well as on manganese acetate concentration in the electrolyte. Catalytic activity of the layers in CO → CO₂ reaction is studied in the static and flow conditions. The manganese-containing layers obtained possess the catalytic activity in CO → CO₂ oxidation reaction at the temperature range of 250-350 °C. The catalytic activity depends on the concentration and surface distribution of manganese as well as on the layers morphology.     

Catalyst formation at various temperatures by hydrogen radical treatment and synthesis of silicon nanowires

Metal nanocrystals as catalyst from a metal oxide film were fabricated at various temperatures after hydrogen radical treatment and great quantities of silicon nanowires (SiNWs) were successfully synthesized using the hydrogen microwave afterglow deposition method. Indium (In) metal nanocrystals with size of about 12 nm were obtained from indium oxide film after hydrogen radical pre-treatment for 5 min at 400 °C and their quantity reached approximately 3 × 10¹⁰ cm⁻². Subsequently, a numerous SiNWs were grown with the crystal diffraction of (1 1 1), (2 2 0) and (3 1 1). The diameters of the SiNWs mainly ranged from 5 to 120 nm and their lengths extended to about 8.5 μm.     

Temperature induced size selective synthesis of hybrid Cds/pepsin nanocrystals and their photoluminescence investigation

There is growing interest in materials chemistry for taking advantage of the physical and chemical properties of biomolecules in the development of next generation nanoscale materials for opto-electronic applications. A biomimetic approach to materials synthesis offers the possibility of controlling size, shape, crystal structure, orientation, and organization. The great progress has been made in the control that can be exerted over optical materials synthesis using biomolecules (protein, nucleic acid)/mineral interfaces as templates for directed synthesis. We have synthesized the CdS nanocrystals using pepsin by biomimetic technique at four different set temperatures. X-ray diffraction (XRD) and small angle X-ray scattering (SAXS) results showed that we are able to tune the size and distribution profile just by tuning the reaction (Rx) temperature and goes towards excitonic Bhor radius (2.5 nm) at low temperature (4 °C). The narrow absorption peak at 260 nm from Cd²⁺-pepsin complex dominates and indicates the size dispersion of the modified CdS nanoparticles are fairly monodisperse. Effective mass approximation (EMA) shows large blue-shift (~1 eV) in the band gap for the cubic phase from bulk hexagonal CdS. The photoluminescence (PL) and photoluminescence excitation (PLE) spectra are dominated by a strong and narrow band-edge emission tunable in the blue region indicating a narrow size distribution. The reduction in PL efficiency is observed when the Rx temperature increases however no change in PLE spectra and temporal profiles of the band-edge PL is observed. At 4 °C, high emission efficiency with shift of PL spectrum in the violet region is observed for 1.7 nm size CdS quantum dots (QDs). Presence of pepsin has slowed the PL decay which is of the order of 100 μs.     

Cobalt-containing nanocomposites based on zeolites of MFI framework type

Here we report the synthesis of cobalt-containing magnetic nanocomposites based on ZSM-5 zeolite and investigation of their magnetic properties. Preparation of the samples was carried out by thermal decomposition of cobalt carbonyl inside zeolite channels. It was shown that Co@ZSM-5 samples possess ferromagnetic behavior at room temperature owing to formation of anisotropic nanostructures in pores of the matrix.     

Thermal conductivity of CoSb3 nano‐composites grown via a novel solvothermal nano‐plating technique

We have utilized a solvothermal nano‐plating technique to grow nano‐structured CoSb₃ directly onto the surface of micron‐sized CoSb₃ particles that were subsequently hot pressed and densified into a homogeneous skutterudite nano‐composite. We herein present results for three samples: a bulk sample to serve as a reference, and two samples with solvothermally grown nano‐structures of 5 wt% and 20 wt%, respectively. All three samples used the same bulk starting materials. The thermal conductivity was measured via two independent techniques (steady state and laser flash) and both show a systematic reduction in the thermal conductivity with an increasing amount of nano‐structures. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Surface plasmon polariton excitation and manipulation by nanoparticle arrays

Using a vectorial dipolar model for multiple surface plasmon-polariton (SPP) scattering [T. Søndergaard, S.I. Bozhevolnyi, Phys. Rev. B 67 (2003) 165405], we investigate the possibility of simultaneous SPP excitation and in-plane manipulation with square-lattice arrays of nanoparticles. The SPP excitation followed by focusing and/or waveguiding of SPP waves is observed with nanoparticle arrays of different shapes, demonstrating the feasibility of the suggested approach.     

High‐temperature stability of Au/p‐type diamond Schottky diode

Rectification properties of Au Schottky diodes were investigated in high‐temperature operation. These diodes were fabricated on a p‐type diamond single crystal using the vacuum‐ultraviolet light/ozone treatment. The ideality factor n of the Schottky diodes decreased monotonically with increasing measurement temperature whereas the Schottky barrier height ?_b increased, and ?_b reached 2.6 eV at 550 K with n of 1.1. Through high temperature heating at 870 K, the mean value of ?_b at 300 K changed permanently from 2.2 eV to 1.1 eV. Decrease of ?_b might originate from a dissolution of oxygen termination at the Au/diamond interface. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Patterned aluminum nanowires produced by electron beam at the surfaces of AlF3 single crystals

Cubic- and rectangular-shape single crystals of α-AlF₃ in sizes of 5-50 μm have been synthesized by a solid-vapor phase process. Using the electron beam induced decomposition of AlF₃, a method is demonstrated for fabricating patterned aluminum nanowires in AlF₃ substrate in a scanning electron microscope. By controlling the accelerating voltage, the beam current and scanning time, it is possible to fabricate metallic nanowires of different sizes. The aluminum nanowires may act as nano-interconnects for nanoelectronics. This work demonstrates a potential technique for e-beam nanofabrication.     

Plasmon energy chemical phase mapping of reactive multilayers

An analytical method of quantitative phase identification and mapping on the nanoscale is presented based on correlative similarity mapping from spectrum images within electron energy loss spectroscopy across the low‐loss plasmon region. The method is applied to map the reaction layer formation for heat treated Cu–Al–Al₂O₃ thin films. Coexistence of residual Al pockets next to polycrystalline but epitaxial CuAl₂ as main reaction product is found as well as a distinctive interfacial plasmon region. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Room temperature photoluminescence from amorphous silicon nanoparticles in SiOx thin films

Amorphous SiO_x thin films with four different oxygen contents (x=1.15, 1.4, 1.5, and 1.7) have been prepared by thermal evaporation of SiO in vacuum and then annealed at 770 or 970 K in argon for various times ?40 min. The influence of annealing conditions and the initial film composition on photoluminescence (PL) from the annealed films has been explored. Intense room temperature PL has been observed from films with x?1.5, visible with a naked eye. It has been shown that PL spectra of most samples consists of two main bands: (i) a ‘green’ band centered at about 2.3 eV, whose position does not change with annealing conditions and (ii) an ‘orange-red’ band whose maximum moves from 2.1 to 1.7 eV with increasing annealing time and temperature and decreasing initial oxygen content. These observations have been explained assuming recombination via defect states in the SiO_x matrix for the first band and emission from amorphous Si nanoparticles for the second one.     

Photocatalytic activity enhancement of TiO2 films by micro and nano-structured surface modification

Titanium oxide thin films were deposited by spin coating using a precursor solution of titanium oxide (IV) acetylacetonate. To increase the contact surface area of the films, TiO₂ microspheres were added to the surface of the films. These spheres were 2 μm in diameter and formed agglomerates on the surface. They did not spread uniformly across the substrate, creating different roughnesses and morphologies along the surface of films. Photocatalytic properties of the samples were tested by the degradation of a methyl orange solution. The degradation performance was compared between plain films, films with microspheres and films covered with commercial TiO₂ P25 powder. The results indicate that the samples that were surface modified with TiO₂ microspheres present a photodegradation reaction rate 62 times higher than that obtained for plain TiO₂ films. The rate of reaction of the samples covered with P25 was 2 times greater than that obtained for the samples with microspheres, but the adhesion to the film was better in the case of microspheres. Moreover, samples with microspheres could be reused several times maintaining the same structural and photocatalytic properties.     

Layer‐by‐layer fabrication of hierarchical structures in sol–gel templated thin titania films

The fabrication of titania nanostructures with hierarchical order of different structural levels is investigated. The nanostructures are prepared with a diblock‐copolymer assisted sol–gel process. By iterative spin‐coating of the solution onto silicon substrates a thin polymer‐nanocomposite film is deposited and transformed to purely anatase titania nanostructures via calcination. In total, this procedure is repeated three times on top of the substrate. The approach is monitored with grazing incidence small angle X‐ray scattering after each fabrication step. With scanning electron microscopy the final hierarchical structure is imaged. From the characterization different structural levels are clearly identified.

     

Catalytic and non-catalytic growth of amorphous silica nanowires and their photoluminescence properties

A simple method based on the thermal oxidation of Si wafers in presence of a mixture of MgO and graphite powder was developed for large-scale synthesis of very long amorphous silica nanowires. The synthesis was done with and without gold as the catalyst. Almost aligned uniform nanowires with diameters within 60-90 nm and length up to few hundred micrometers were obtained using gold as the catalyst while bicycle chain like nanowires were obtained in absence of the catalyst. The growth sequence of the nanowires was observed through scanning electron microscope. Both forms of the nanowires emitted blue lights at 414 nm (3 eV) under excitation at 250 nm.     

GISAXS study of carbon nanotubes grown by CVD

We report a quantitative Grazing Incidence Small Angle X‐ray Scattering (GISAXS) study of a dense film of mutually oriented carbon nanotubes (CNTs) grown by a catalytically‐activated DC HF CCVD process after dispersion of metallic catalytic (Co) islands on SiO₂/Si(100) substrates. The GISAXS pattern analysis is expanded to non‐correlated surface science systems and is based on CNTs density, characteristic lengths, atomic Co dispersion throughout the CNTs and roughnesses of uncorrelated particles. The results are closely compared to SEM and TEM observations. The GISAXS patterns, even dominated by envelope features of disordered objects, provide significant complementary quantitative data about CNTs films. The results underline that cobalt continuously fills the nanotube in the course of the growth and that the CNTs experience a large tendency toward mutual alignment. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)