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.

Straightforward synthesis of bimetallic Co/Pt nanoparticles in ionic liquid: atomic rearrangement driven by reduction-sulfidation processes and Fischer-Tropsch catalysis.

Unsupported bimetallic Co/Pt nanoparticles (NPs) of 4.4 ± 1.9 nm can be easily obtained by a simple reaction of [bis(cylopentadienyl)cobalt(ii)] and [tris(dibenzylideneacetone) bisplatinum(0)] complexes in 1-n-butyl-3-methylimidazolium hexafluorophosphate IL at 150 °C under hydrogen (10 bar) for 24 h. These bimetallic NPs display core-shell like structures in which mainly Pt composes the external shell and its concentration decreases in the inner-shells (CoPt3@Pt-like structure). XPS and EXAFS analyses show the restructuration of the metal composition at the NP surface when they are subjected to hydrogen and posterior H2S sulfidation, thus inducing the migration of Co atoms to the external shells of the bimetallic NPs. Furthermore, the isolated bimetallic NPs are active catalysts for the Fischer-Tropsch synthesis, with selectivity for naphtha products.

Photocatalytic hydrogen production of Co(OH)2 nanoparticle-coated α-Fe2O3 nanorings.

The production of hydrogen from water using only a catalyst and solar energy is one of the most challenging and promising outlets for the generation of clean and renewable energy. Semiconductor photocatalysts for solar hydrogen production by water photolysis must employ stable, non-toxic, abundant and inexpensive visible-light absorbers capable of harvesting light photons with adequate potential to reduce water. Here, we show that α-Fe2O3 can meet these requirements by means of using hydrothermally prepared nanorings. These iron oxide nanoring photocatalysts proved capable of producing hydrogen efficiently without application of an external bias. In addition, Co(OH)2 nanoparticles were shown to be efficient co-catalysts on the nanoring surface by improving the efficiency of hydrogen generation. Both nanoparticle-coated and uncoated nanorings displayed superior photocatalytic activity for hydrogen evolution when compared with TiO2 nanoparticles, showing themselves to be promising materials for water-splitting using only solar light.

Controlled synthesis of Mn3O4 nanoparticles in ionic liquids.

This work describes a simple one-step synthesis of Mn3O4 nanoparticles by thermal decomposition of [Mn(acac)2] (acac = acetylacetonate) using imidazolium ionic liquids (ILs) and a conventional solvent, oleylamine, for comparison. The Mn3O4 nanoparticles were characterized by XRD, ATR-FTIR, TEM, Raman, UV/VIS and magnetometry techniques. The addition of 1-n-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide IL (BMI·NTf2) yielded a smaller particle size (9.9 ± 1.8 nm) with better dispersion and more regular sizes than synthesis using oleylamine as the solvent (12.1 ± 3.0 nm). The complete conversion of the precursor to Mn3O4 nanoparticles occurred after 96 h at 180 °C for the reaction performed in BMI·NTf2. However, under these reaction conditions in oleylamine, no precursor was detected, but two different phases were observed: a major phase corresponding to Mn3O4 and a minor phase corresponding to MnO2. Magnetometry revealed that Mn3O4 nanoparticles synthesized in either oleylamine or BMI·NTf2 exhibited ferrimagnetic behavior at low temperatures, whereas they were paramagnetic at room temperature. As expected, the blocking temperature and the coercivity decreased with the size of nanoparticles. Our results demonstrate that reaction conditions such as time, and the nature of the ionic liquid play important roles in determining the size of Mn3O4 nanoparticles.