Electrodeposition of catalytic and magnetic gold nanoparticles on dendrimer-carbon nanotube layer-by-layer films

Magnetic and catalytic gold nanoparticles were electrodeposited through potential pulse on dendrimer-carbon nanotube layer-by-layer (LbL) films. A plasmon absorption band at about 550 nm revealed the presence of nanoscale gold in the film. The location of the Au nanoparticles in the film was clearly observed by selecting the magnetic force microscopy mode. To our knowledge, this is the first report on the electrochemical synthesis of magnetic Au nanoparticles. In addition to the magnetic properties, the Au nanoparticles also exhibited high catalytic activity towards ethanol and glycerol oxidation in alkaline medium.

Analysis of dispersive and dissipative media with optical resonances

In this paper we analyze the problem of light-matter interaction when absorptive resonances are imbedded in the material dispersion. We apply an improved approach to aluminum (Al) in the optical frequency range to investigate the impact of these resonances on the operating characteristics of Al-based nanoscale devices. Quantities such as group velocity, stored energy density, and energy velocity, normally obtained using a single resonance model [Wave Propagation and Group Velocity (Academic Press, 1960), Nat. Mater. 11, 208 (2012)], are now accurately calculated regardless of the medium adopted. We adapt the Loudon approach [Nat. Mater. 11, 208 (2012)] to media with several optical resonances and present the details of the extended model. We also show pertinent results for Al-based metal-dielectric-metal (MDM) waveguides, around spectral resonances. The model delineated here can be applied readily to any metal accurately characterized by Drude-Lorentz spectral resonance features. (C) 2012 Optical Society of America

Tailoring Molecular Architectures with Cobalt Tetrasulfonated Phthalocyanine: Immobilization in Layer-by-Layer Films and Sensing Applications

In the field of organic thin films, manipulation at the nanoscale can be obtained by immobilization of different materials on platforms designed to enhance a specific property via the layer-by-layer technique. In this paper we describe the fabrication of nanostructured films containing cobalt tetrasulfonated phthalocyanine (CoTsPc) obtained through the layer-by-layer architecture and assembled with linear poly(allylamine hydrochloride) (PAH) and poly(amidoamine) dendrimer (PAMAM) polyelectrolytes. Film growth was monitored by UV-vis spectroscopy following the Q band of CoTsPc and revealed a linear growth for both systems. Fourier transform infrared (FTIR) spectroscopy showed that the driving force keeping the structure of the films was achieved upon interactions of CoTsPc sulfonic groups with protonated amine groups present in the positive polyelectrolyte. A comprehensive SPR investigation on film growth reproduced the deposition process dynamically and provided an estimation of the thicknesses of the layers. Both FTIR and SPR techniques suggested a preferential orientation of the Pc ring parallel to the substrate. The electrical conductivity of the PAH films deposited on interdigitated electrodes was found to be very sensitive to water vapor. These results point to the development of a phthalocyanine-based humidity sensor obtained from a simple thin film deposition technique, whose ability to tailor molecular organization was crucial to achieve high sensitivity.

Synthesis of supported metal nanoparticle catalysts using ligand assisted methods

The synthesis and characterization methods of metal nanoparticles (NPs) have advanced greatly in the last few decades, allowing an increasing understanding of structure-property-performance relationships. However, the role played by the ligands used as stabilizers for metal NPs synthesis or for NPs immobilization on solid supports has been underestimated. Here, we highlight some recent progress in the preparation of supported metal NPs with the assistance of ligands in solution or grafted on solid supports, a modified deposition-reduction method, with special attention to the effects on NPs size, metal-support interactions and, more importantly, catalytic activities. After presenting the general strategies in metal NP synthesis assisted by ligands grafted on solid supports, we highlight some recent progress in the deposition of pre-formed colloidal NPs on functionalized solids. Another important aspect that will be reviewed is related to the separation and recovery of NPs. Finally, we will outline our personal understanding and perspectives on the use of supported metal NPs prepared through ligand-assisted methods.

Spectroscopic, morphological and electrochromic characterization of layer-by-layer hybrid films of polyaniline and hexaniobate nanoscrolls

The combination of semiconducting oxides and polyaniline in the nanoscale range may result in hybrid materials having enhanced properties, such as electrochromism and charge capacity. This paper reports the spectroscopic, morphological and electrochromic characterization of hybrid films made up of hexaniobate one-dimensional (1D) nanoscrolls and polyaniline prepared by the layer-by-layer assembly technique (LbL). Secondary electron imaging and backscattered electron imaging techniques performed using a scanning electron microscope showed that polyaniline is adsorbed on the hexaniobate nanoscrolls, which confirms the combination of the components in the nanoscale domain. UV-VIS-NIR electronic spectra of the LbL hybrid films showed the absorption tail in the NIR region, assigned to delocalized polarons of the polyaniline. Resonance Raman spectra in the 1000-1700 cm(-1) range indicated that hybrid films present a higher relative intensity of polaron bands at 1337 and 1508 cm(-1) than pristine polyaniline in the emeraldine salt form. These results suggest that hexaniobate nanoscrolls induce a secondary doping of polyaniline. The cyclic voltammetry (CV) data for the hybrid film showed a specific capacity of 870 C cm(-3). According to CV results, the synergistic effect on charge storage properties of the hybrid material is attributed to the enhanced electroactivity of the hexaniobate component in the LbL film. Spectroelectrochemical experiments showed that the electrochromic efficiencies at 420 nm are ca. -41 and 24 cm(2) C-1 as the potential changes from 0.8 to -0.9 V and from -0.9 to -1.8 V, respectively, whereas at 800 nm the efficiencies are ca. -55 and 8 cm(2) C-1 for the same potential ranges. The electrochromic efficiencies and multi-colour character of the LbL film of hexaniobate nanoscrolls and polyaniline indicate that this novel hybrid material is an interesting modified electrode for electrochromic devices.

Electronic and magnetic properties of SnO2/CrO2 thin superlattices

In this article, using first-principles electronic structure calculations within the spin density functional theory, alternated magnetic and non-magnetic layers of rutile-CrO2 and rutile-SnO2 respectively, in a (CrO2) n (SnO2) n superlattice (SL) configuration, with n being the number of monolayers which are considered equal to 1, 2, ..., 10 are studied. A half-metallic behavior is observed for the (CrO2) n (SnO2) n SLs for all values of n. The ground state is found to be FM with a magnetic moment of 2 μB per chromium atom, and this result does not depend on the number of monolayers n. As the FM rutile-CrO2 is unstable at ambient temperature, and known to be stabilized when on top of SnO2, the authors suggest that (CrO2) n (SnO2) n SLs may be applied to spintronic technologies since they provide efficient spin-polarized carriers.

Study of the vertical transport in p-doped superlattices based on group III-V semiconductors

The electrical conductivity σ has been calculated for p-doped GaAs/Al0.3Ga0.7As and cubic GaN/Al0.3Ga0.7N thin superlattices (SLs). The calculations are done within a self-consistent approach to the k → ⋅ p → theory by means of a full six-band Luttinger-Kohn Hamiltonian, together with the Poisson equation in a plane wave representation, including exchange correlation effects within the local density approximation. It was also assumed that transport in the SL occurs through extended minibands states for each carrier, and the conductivity is calculated at zero temperature and in low-field ohmic limits by the quasi-chemical Boltzmann kinetic equation. It was shown that the particular minibands structure of the p-doped SLs leads to a plateau-like behavior in the conductivity as a function of the donor concentration and/or the Fermi level energy. In addition, it is shown that the Coulomb and exchange-correlation effects play an important role in these systems, since they determine the bending potential.