An effective approach for modifying carbonaceous materials with niobium single sites to improve their catalytic properties.

In this paper we show a very simple route for the incorporation of catalytically active niobium species on the surface of carbon materials, such as graphene oxide, carbon nanotubes and activated carbon. Some existing methods of incorporating a transition metal on a support have involved co-precipitation or wet impregnation, to obtain the corresponding oxides. These methods, however, cause reduction in the specific area of the support and can also form large metal oxide particles with loss of metal exposure. Therefore, here we present a novel way to add catalytically active species on the surfaces of different types of carbon through the formation of interaction complexes between the metal precursor and the functional groups of the carbon matrix. Because of the excellent catalytic properties exhibited by the niobium species we choose the NH4[NbO(C2O4)2(H2O)2]·2H2O salt as the model precursor. The characterization by XPS reveals the presence of the niobium species indicated by the displacement of the peaks between 206-212 eV related to the oxalate species according to the spectrum from pure niobium oxalate. Images obtained by TEM and SEM show the typical morphologies of carbonaceous materials without the niobium oxide formation signal, which indicates the presence of niobium complexes as isolated sites on the carbon surfaces. This new class of materials exhibited excellent properties as catalysts for pollutant oxidation. The presence of Nb promotes the catalytic activation of H2O2 generating hydroxyl radicals in situ, which allows their use in the organic compound oxidation processes. Tests for DBT oxidation indicate that Nb significantly improves the removal of such pollutants in biphasic reactions with removal around 90% under the tested conditions. Theoretical calculations showed that the most favorable adsorption model is an ionic complex presenting a ΔG = -108.7 kcal mol(-1) for the whole adsorption process.

Characterization of the Dynamics of Photoluminescence Degradation in Aqueous CdTe/CdS Core-Shell Quantum Dots.

We investigate the effects of the excitation power on the photoluminescence spectra of aqueous CdTe/CdS core-shell quantum dots. We have focused our efforts on nanoparticles that are drop-cast on a silicon nitride substrate and dried out. Under such conditions, the emission intensity of these nanocrystals decreases exponentially and the emission center wavelength shifts with the time under laser excitation, displaying a behavior that depends on the excitation power. In the low-power regime a blueshift occurs, which we attribute to photo-oxidation of the quantum dot core. The blueshift can be suppressed by performing the measurements in a nitrogen atmosphere. Under high-power excitation the nanoparticles thermally expand and aggregate, and a transition to a redshift regime is then observed in the photoluminescence spectra. No spectral changes are observed for nanocrystals dispersed in the solvent. Our results show a procedure that can be used to determine the optimal conditions for the use of a given set of colloidal quantum dots as light emitters for photonic crystal optical cavities.

Phase-dependent premelting of self-assembled phosphonic acid multilayers.

Melting and premelting phenomena in self-organized organic systems have been extensively explored in the literature, exploring distinct behaviors of different molecule lengths and morphologies. Nevertheless, the influence of the supramolecular assembly configuration on the occurrence of premelting remains poorly explored. Here we use phosphonic acids as model systems for self-organized molecular assemblies. These molecules exhibit long-range order on different types of substrates. The balance between chain-to-chain and head-to-head interactions leads to distinct types of stackings. Although their structural configurations are well understood, very little is known about their behavior near the melting transition. We show here that premelting occurs in lamellar structures and that its behavior depends directly on the ordered configuration assumed in the studied multilayers. Two molecules with different chain lengths were investigated: octadecyl phosphonic and octyl phosphonic acids. Although almost no dependence on the molecule length was observed, the occurrence of premelting is strongly influenced by their lamellar packing configuration. For tilted packings premelting is unfavored while in straight configurations, where alkyl chain interactions are weakened with respect to head-to-head interactions, strong premelting is observed. We find that the onset of premelting occurs at the domain boundaries with straight lamellar configurations and the domain sizes exhibit power law temperature dependences.

Correlation between (in)commensurate domains of multilayer epitaxial graphene grown on SiC(0001) and single layer electronic behavior.

A systematic study of the evolution of the electronic behavior and atomic structure of multilayer epitaxial graphene (MEG) as a function of growth time was performed. MEG was obtained by sublimation of a 4H-SiC(0001(-)) substrate in an argon atmosphere. Raman spectroscopy and x-ray diffraction were carried out in samples grown for different times. For 30 min of growth the sample Raman signal is similar to that of graphite, while for 60 min the spectrum becomes equivalent to that of exfoliated graphene. Conventional x-ray diffraction reveals that all the samples have two different (0001) lattice spacings. Grazing incidence x-ray diffraction shows that thin films are composed of rotated (commensurate) structures formed by adjacent graphene layers. Thick films are almost completely disordered. This result can be directly correlated to the single layer electronic behavior of the films as observed by Raman spectroscopy. Finally, to understand the change in lattice spacings as a result of layer rotation, we have carried out first principles calculations (using density functional theory) of the observed commensurate structures.

Metastable phase formation and structural evolution of epitaxial graphene grown on SiC(100) under a temperature gradient.

Multilayer epitaxial graphene was obtained from a 6H-SiC(001) substrate subjected to a temperature gradient from 1250 to 1450 °C. Scanning tunneling microscopy and x-ray diffraction were used to identify the structure and morphology of the surface, from which the formation of a metastable phase was inferred. By a comparison between microscopy and diffraction data, we report the appearance of misoriented Si-doped graphene in cold regions (1250 °C) of the substrate. This metastable phase occurs in domains where silicon sublimation is incomplete and it coexists with small domains of epitaxial graphene. At 1350 °C this phase disappears and one observes complete graphene-like layers (although misoriented), where rotational registry between the underlying epitaxial graphene and additional layers is absent. At 1450 °C the stacking among layers is established and the formation of highly oriented single crystalline graphite is complete. The stability of this Si-rich metastable phase at 1250 °C was confirmed by first-principles calculations based on the density functional theory.

The influence of oxygen-containing functional groups on the dispersion of single-walled carbon nanotubes in amide solvents.

Surface composition plays an important role in carbon nanotube dispersibility in different environments. Indeed, it determines the choice of dispersion medium. In this paper the effect of oxidation on the dispersion of HiPCO single-walled carbon nanotubes (SWNTs) in N-methyl-pyrrolidinone (NMP), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), N-dodecyl-pyrrolidinone (N12P) and cyclohexyl-pyrrolidinone (CHP) was systematically studied. During the oxidation process, similar amounts of carboxylic acid and phenolic groups were introduced to mostly already existing defects. For each solvent the dispersion limits and the absorption coefficients were estimated by optical absorption analysis over a range of SWNT concentrations. The presence of acid oxygenated groups increased SWNT dispersibility in NMP, DMF and DMA, but decreased in N12P and CHP. The absorption coefficients, however, decreased for all solvents after oxidation, reflecting the weakening of the effective transition dipole of the π-π transition with even limited extension functionalization and solvent interaction. The analysis of the results in terms of Hansen and Flory-Huggins solubility parameters evidenced the influence of dipolar interactions and hydrogen bonding on the dispersibility of oxidized SWNTs.

Nanowires and nanoribbons formed by methylphosphonic acid.

The production and physical properties of nanowires and nanoribbons formed by methylphosphonic acid (MPA)--CH3PO(OH)2--were investigated. These structures are formed on an aluminum coated substrate when immersed in an ethanolic solution of MPA for several days. A careful investigation of the growth conditions resulted in a narrow window of solution concentrations and temperatures for the successful development of nanowires and nanoribbons. Several different techniques were employed to characterize these nanostructures: (1) Photoluminescence experiments showed a strong emission at 2.3 eV (green), which is visible to the naked eye; (2) X-ray diffraction experiments indicated a significant cristalinity, in agreement with atomic force microscopy (AFM) and transmission electron microscopy (TEM) morphology images, which show organized nano-scale wires and ribbons, (furthermore, AFM-Phase and TEM images also suggest that nanoribbons are formed by well-aligned nanowires); (3) Conductive-AFM experiments revealed an intermediary conductivity for these structures (10(-1)/Ohm x m), which is similar to some intrinsic semiconductors and; (4) finally, Infrared, Raman, and X-Ray Photoelectron Spectroscopies produced information about the contents, structure, and composition of both wires and ribbons.

3D composition of epitaxial nanocrystals by anomalous X-ray diffraction: observation of a Si-rich core in Ge domes on Si(100).

Three-dimensional composition maps of nominally pure Ge domes grown on Si(001) at 600 degrees C were obtained from grazing incidence anomalous x-ray scattering data at the Ge K edge. The data were analyzed in terms of a stack of layers with laterally varying concentration. The results demonstrated that the domes contained a Si-rich core covered by a Ge-rich shell and were independently supported by selective etch experiments. The composition profile resulted from substrate Si alloying into the Ge during growth to partially relax the stress in and under the domes.