Teresa Valdés-Solís

Shape and Size Effects of ZnO Nanocrystals on Photocatalytic Activity

A wet-chemical method was employed to prepare zinc oxide nanocrystals having controlled morphology through thermal decomposition of a zinc precursor in self-assembled supramolecular structures in solvent under mild conditions. This solution method offers finer tailoring of the size and shape of the nanocrystals and is complementary to most reported physical methods. Understanding the morphological effects of pure or modified zinc oxide nanocrystals on photocatalytic activity is important in regard to enhanced solar energy capture and utilization but has been scarcely addressed in the past. The photocatalytic rate was found to have no dependence on ZnO particle size, but the shape factor seems to be of overriding importance. Hexagonal platelike nanocrystals were found to display at least 5 times higher activity than rod-shaped crystals, which clearly suggests that the polar (001) and (001) faces are more active surfaces than the nonpolar surfaces perpendicular to them.

Low-temperature SCR of NOx with NH3 over carbon-ceramic supported catalysts

A new method for preparing vanadium oxide supported on carbon-ceramic cellular monoliths is described. This includes a support oxidation step with HNO3, followed by ionic exchange with a NaOH solution, equilibrium adsorption impregnation of VO 2+ and thermal treatment. As a result an active catalyst for low-temperature selective catalytic reduction (SCR) reaction is obtained. The V-catalyst is more resistant to SO2 poisoning than the previously developed Mn-catalyst. Inhibition by water is reversible for both types of catalysts. Testing of the vanadium catalyst after subjecting it to the outlet gas stream of a power plant shows fast deactivation until constant residual activity is reached. Deactivation seems to be caused by arsenic poisoning and the formation of superficial sulphates.

Understanding Gas-Induced Structural Deformation of ZIF-8.

ZIF-8 is a zeolitic imidazolate framework with very good thermal and chemical stability that opens up many applications that are not feasible by other metal-organic frameowrks (MOFs) and zeolites. Several works report the adsorption properties of ZIF-8 for strategic gases. However, despite the vast experimental corpus of data reported, there seems yet to be a dearth in the understanding of the gas adsorption properties. In this work we provide insights at a molecular level on the mechanisms governing the ZIF-8 structural deformation during molecular adsorption. We demonstrate that the ZIF-8 structural deformation during the adsorption of different molecules at cryogenic temperature goes beyond the gas-induced rotation of the imidazolate linkers. We combine experimental and simulation studies to demonstrate that this deformation is governed by the polarizability and molecular size and shape of the gases, and that the stepped adsorption behavior is defined by the packing arrangement of the guest inside the host.

Stainless steel wire mesh-supported ZnO for the catalytic photodegradation of methylene blue under ultraviolet irradiation

The aim of this study was to assess the activity of catalysts formed by nanostructured zinc oxide supported on stainless steel wire mesh for the photocatalytic degradation of methylene blue under UV irradiation. Catalysts prepared by means of different low temperature synthesis methods, as described in a previous work (Vu et al., Mater. Res. Bull. 47 (2012) 1577-1586) were tested. A new activity parameter was introduced in order to compare the catalytic activity of the different catalysts. The best catalyst showed a catalytic activity higher than that of the reference material TiO(2) P25 (Degussa-Evonik). This high activity is attributed to a higher quantum yield derived from the small particle length of the ZnO deposited on the wire mesh. The photocatalytic degradation kinetics of methylene blue fitted a potential model with n orders ranging from 0.5 to 6.9. Reaction orders over 1 were attributed to catalyst deactivation during the reaction resulting from the photocorrosion of ZnO.

Solid-phase synthesis of graphitic carbon nanostructures from iron and cobalt gluconates and their utilization as electrocatalyst supports

We present a novel and facile synthesis methodology for obtaining graphitic carbon structures from Fe(II) and Co(II) gluconates. The formation of graphitic carbon can be carried out in only one step by means of heat treatment of these organic salts at a temperature of 900 degrees C or 1000 degrees C under inert atmosphere. This process consists of the following steps: (a) pyrolysis of the organic gluconate and its transformation to amorphous carbon, (b) conversion of Fe(2+) and Co(2+) ions to Fe(2)O(3) and CoO and their subsequent reduction to metallic nanoparticles by the carbon and (c) conversion of a fraction of formed amorphous carbon to graphitic structures by Fe and Co nanoparticles that act as catalysts in the graphitization process. The removal of the amorphous carbon and metallic nanoparticles by means of oxidative treatment (KMnO(4) in an acid solution) allows graphitic carbon nanostructures (GCNs) to be selectively recovered. The GCNs thus obtained (i.e. nanocapsules and nanopipes) have a high crystallinity as evidenced by TEM/SAED, XRD and Raman analysis. In addition, we used these GCNs as supports for platinum nanoparticles, which were well dispersed (mean Pt size approximately 2.5-3.2 nm). Most electrocatalysts prepared in this way have a high electrocatalytical surface area, up to 90 m(2) g(-1) Pt, and exhibit high catalytic activities toward methanol electrooxidation.

Signatures of clustering in superparamagnetic colloidal nanocomposites of an inorganic and hybrid nature.

The individual and co-operative properties of inorganic and hybrid superparamagnetic colloidal nanocomposites that satisfy all the requirements of magnetic carriers in the biosciences and/or catalysis fields are been studied. Essential to the success of this study is the selection of suitable synthetic routes (aerosol and nanocasting) that allow the preparation of materials with different matrix characteristics (carbon, silica, and polymers with controlled porosity). These materials present magnetic properties that depend on the average particle size and the degree of polydispersity. Finally, the analysis of the co-operative behavior of samples allows for the detection of signatures of clustering, which are closely related to the textural characteristics of samples and the methodology used to produce the magnetic carriers.

Mechanism of low temperature selective catalytic reduction of NO with NH3 over carbon-supported Mn3O4

In this work, the interactions at low temperature (125 °C) of gaseous NH3, NO and O2 with carbon-supported manganese oxide catalysts have been extensively studied, mainly via step–response experiments, with the objective of explaining the low-temperature mechanism of the SCR reaction on such catalysts. To achieve this aim, the present work analyses the active phase and the interaction of NO species with the active phase both in the absence and in the presence of O2. The catalyst was found to be Mn3O4 composed locally of octahedral Mn2O3 and a slightly oxidised (oxygen excess) tetrahedral MnO. Both local species have different though interrelated roles during the SCR process. On the octahedral Mn2O3 NO can be adsorbed as nitrosyls (on oxygen vacancies) and as linear and bridged nitrites on oxygen atoms (absent under steady state SCR conditions). On the tetrahedral MnO NO2 is adsorbed as nitrates on hydroxyl groups previously formed by the reaction of water with the oxygen excess of this phase. NO2 is produced via the reaction of nitrosyls with O2. These nitrates are responsible for the partial deactivation of the catalyst under SCR conditions.

Fabrication of mesoporous SiO2–C–Fe3O4/γ–Fe2O3 and SiO2–C–Fe magnetic composites

A synthetic method for the fabrication of silica-based mesoporous magnetic (Fe or iron oxide spinel) nanocomposites with enhanced adsorption and magnetic capabilities is presented. The successful in situ synthesis of magnetic nanoparticles is a consequence of the incorporation of a small amount of carbon into the pores of the silica, this step being essential for the generation of relatively large iron oxide magnetic nanocrystals ( approximately 10+/-3nm) and for the formation of iron nanoparticles. These composites combine good magnetic properties (superparamagnetic behaviour in the case of SiO(2)-C-Fe(3)O(4)/gamma-Fe(2)O(3) samples) with a large and accessible porosity made up of wide mesopores (>9nm). In the present work, we have demonstrated the usefulness of this kind of composite for the adsorption of a globular protein (hemoglobin). The results obtained show that a significant amount of hemoglobin can be immobilized within the pores of these materials (up to 180mgg(-1) for some of the samples). Moreover, we have proved that the composite loaded with hemoglobin can be easily manipulated by means of an external magnetic field.

Cyanide and Phenol Oxidation on Nanostructured Co3O4 Electrodes Prepared by Different Methods

Financial support by the Generalitat Valenciana grant no. GV05/136, no. GV06/106, and no. RED ARVIV/2007/076) and Ministerio de Educacion y Ciencia (MAT2007-60621 and MAT2005-00262) projects.

Controlled release of precipitating agents through solvothermal destabilization of microemulsions: one-pot synthesis of monoclinic zirconia nanostructures

We report a versatile one-step multiphase approach to control size, crystallinity and assembly at the nanoscale. The method takes advantage of the controlled release of precipitating agents achieved through the solvothermal destabilization of reverse microemulsions. This method permits the preparation of nanoparticles (as an example we prepare zirconia materials) self-assembled in open (palmate leaf-like) and compact nanostructures that could be easily processed using existing solution routes. The mechanisms of formation of these nanostructures are presented on the basis of the structural information and surface charge data provided by various techniques. The morphology of the nanostructures is found to be the combined result of several growth features, among which self-assembly driven by electrostatic forces plays a critical role. In addition, we have found that more open nanostructures lead to monoclinic zirconia samples with a higher degree of crystallinity, which supports the idea that surface energy must play a critical role in the stabilization of tetragonal polymorphs or amorphous zirconia phases.