Geonel Rodríguez-Gattorno

CeO2 thin films by flash evaporation

Oxide ion conductors have received special attention during the last 20 years for their applications in high temperature fuel cells and sensors. Cerium oxide based solid electrolytes have one of the lowest activation energies among the fluorite type oxide ion conductors. We present a methodology for obtaining cerium oxide thin films by flash evaporation. The films were characterized using X-ray diffraction, optical absorption, and AC conductivity. The results show the ionic nature of the electrical conductivity.

The nucleation kinetics of ZnO nanoparticles from ZnCl2 in ethanol solutions

The first stages of the synthesis of ZnO nanoparticles by forced hydrolysis of ZnCl2 with NaOH and water in ethanol have been investigated using UV-Vis spectrophotometry. At sufficiently low water concentrations, focusing of the nanoparticle size distribution was observed during the nucleation and growth phase, followed by a defocusing phase when coarsening becomes significant. During nucleation and growth, only the smaller particles grow while the larger particles have an essentially zero growth rate, indicating that the growth rate decreases rapidly with particle size. As the average particle size remains nearly constant in this regime, the absorbance increase with time can be used to determine the nucleation rate. The nucleation rate was found to depend on both the water concentration and the reactant concentrations. The results are discussed in terms of a mechanism where water determines the precursor formation kinetics thus controlling the nucleation rate.

Hierarchically Nanostructured Barium Sulfate Fibers

BaSO(4) nanostructures with controlled morphologies were successfully produced via one-step process through precipitation of BaSO(4) in aqueous and organic media. The synthesis is carried out by mixing solutions of BaCl(2) and Na(2)SO(4) in presence of EDTA (disodium ethylenediaminetetraacetic acid) at room temperature. The influence of the reaction conditions such as initial reactants concentration, pH, EDTA/[Ba(2+)] ratio and aging on the BaSO(4) nanoparticles organization is studied. Using EDTA in aqueous media, spherical secondary particles of 500 nm diameter are obtained, which are formed by 4 nm size primary particles. With dimethyl sulfoxide and small amounts of water (5%) and EDTA, the aging process allows the production of long homogeneous fibers, related to hierarchical organization of BaSO(4) nanoparticles. Direct observation of self-assembling of primary particles by HRTEM allows proposing a mechanism for fiber formation, which is based on multipolar attractions that lead to a brick-by-brick organization along a preferential orientation. Results evidence the role of EDTA as controlling agent of the morphology and primary and secondary mean particle size.

Synthesis and Thermal Behavior of Metallic Cobalt Micro and Nanostructures

In this contribution, a comparative study of metallic cobalt micro and nanoparticles obtained in solution by four different chemical routes is reported. Classic routes such as borohydride reduction in aqueous media and the so-called polyol methodology were used to obtain the cobalt nanostructures to be studied. Using CTAB as surfactant, cobalt hollow nanostructures were obtained. The use of strong reducing agents, like sodium borohydride, favors the formation of quasi-monodispersed nanoparticles of about 2 nm size but accompanied with impurities; for hydrazine (a mild reducer), nanoparticles of larger size are obtained which organize in spherical microagglomerates. Valuable information on the particles thermal stability and on nature of the species anchored at their surface was obtained from thermogravimetric curves. The samples to be studied were characterized from UV-vis, IR, X-ray diffraction, and electron microscopy images (scanning and transmission).

Influence of morphology on the performance of ZnO-based dye-sensitized solar cells

ZnO nanomaterials with different morphologies, obtained by a sonochemical synthesis method at pH values of 5.5, 8, 10 and 12, have been used as starting materials for the fabrication of dye-sensitized solar cells. The morphology of the nanomaterials and the texture of the films deposited using screen printing depend on the synthesis pH, and the various exposed surface facets interact in a different manner with the dye and electrolyte solutions. The best cell performance was obtained with the morphology that resulted from the synthesis at pH 10, where the {100} and {110} crystal forms are predominant, and where dye coverage was largest. Interestingly, the BET total surface area was lowest for this nanomaterial illustrating the importance of morphology. The influence of the synthesis pH was also evident in the energetics and recombination kinetics of the solar cells. For the ZnO material synthesized at pH 5.5, the band edges appear to be shifted to more negative potentials, which could have resulted in a larger open circuit potential based on thermodynamic considerations. However, the electron life time for the pH 5.5 ZnO material is significantly smaller than for the other three synthesis pH values, indicating that the recombination kinetics are significantly faster for these cells as well, resulting in a smaller open circuit potential based on kinetics arguments. The balance between these two effects determines the experimentally observed open circuit potential. Overall, the results indicate that the dependence of the dye adsorption characteristics on ZnO nanomaterial morphology and film texture are the dominating factors that determine the solar cell performance.

Dehydration Process of Hofmann-Type Layered Solids

In the present work the dehydration process of layered solids with formula unit M(H2O)2[Ni(CN)4]·nH2O, M = Ni, Co, Mn; n = 1, 2, 4 is studied using modulated thermogravimetry. The results show that water molecules need to overcome an energetic barrier (activation energy between 63 and 500 kJ/mol) in order to diffuse through the interlayer region. The related kinetic parameters show a dependence on the water partial pressure. On the other hand, X-ray diffraction results provide evidence that the dehydration process is accompanied by framework collapse, limiting the structural reversibility, except for heating below 80 °C where the ordered structure remains. Removal of water molecules from the interlayer region disrupts the long-range structural order of the solid.

Synthesis and characterization of TiO2 nanoparticles: anatase, brookite, and rutile

Titanium dioxide nanoparticles have been prepared by solution-phase methods in the three phases that occur naturally, anatase, rutile, and brookite. The amorphous titania starting material was prepared from titanium(IV) iso-propoxide using iso-propanol as solvent and a small quantity of water. The resulting material was treated hydrothermally in an acid digestion vessel at temperatures between 175 °C and 230 °C with different reactants to obtain the three phases or controlled mixtures of two phases. The nanomaterials were characterized by a variety of techniques, including X-ray diffraction, Raman spectroscopy, electron microscopy, dynamic light scattering, and UV-Vis absorbance spectrophotometry. The results illustrate the relation between the properties of the nanoparticles in the colloid, in the powder, and in nanostructured thin films prepared with the materials. A thorough understanding of synthesis methods is essential for the preparation of nanomaterials with tailored structural, morphological, and ultimately, physical properties.