Scientific Papers in SCI


Title: Critical thickness and nanoporosity of TiO2 optical thin films
Author(s): Borras, A; Alvarez, R; Sanchez-Valencia, JR; Ferrer, J; Gonzalez-Elipe, AR
Source: Microscopy and Microanalysis, 18 (2012) 1-9

abstract | fulltext

This work reports on the porosity and refraction index of TiO2 thin films as a function of the film thickness. Samples were fabricated by plasma enhanced chemical vapor deposition (PECVD) in a microwave electron cyclotron resonance (MW-ECR) reactor at room temperature using titanium tetra-isopropoxide (MP) as precursor. Experimental parameters such as plasma gas composition (pure oxygen and argon/oxygen mixtures) and pressure (either ECR conditions or "normal" pressure, i.e. 10(-4) or 10(-3) torrs correspondently) were varied. The evolution of the thin film microstructure, porosity and optical properties is critically studied by AFM, SEM, water adsorption isotherms, ellipsometry and UV-Vis transmittance and the existence of a certain critical thickness (t(c)) demonstrated. The porosity of the films with thicknesses ranging from several tens of nanometers up to half a micrometer is evaluated by QCM-isotherms at room temperature. The dependency of this critical thickness with the plasma conditions is evaluated experimental and theoretically. Thus, the microstructure change at t(c) is attributed to a transition from a surface diffused dominated growth mechanism for t < t(c) to another where shadowing is predominant. Dynamic scaling analysis of the two regimes and their Monte Carlo simulation complete the reported study.

September, 2012 | DOI: 10.1016/j.micromeso.2012.04.035

Title: Rapid microwave-assisted synthesis of one-dimensional silver–H2Ti3O7 nanotubes
Author(s): Rodriguez-Gonzalez, V; Obregon-Alfaro, S; Lozano-Sanchez, LM; Lee, SW
Source: Journal of Molecular Catalysis A-Chemical, 353 (2012) 163-170

abstract | fulltext

The formation of silver hydrogen trititanate nanotubes, based on the controllable microwave-assisted hydrothermal nanocrystalline TiO2 transition, was investigated by means of XRD, UV–vis–DRS, Raman, FESEM and HRTEM. The results show that the rapid formation of H-trititanate nanotubes is achieved by self-assemblage of silver nanoparticles in which the lamellar intermediates react with NaOH in hydrothermal conditions. The presence of Ag° nanoparticles in the precursor promotes rapid and more complete formation of layered H2Ti3O7 nanotubes. After reacting for 4 h without subsequent thermal treatment, the inner diameters of the cylinder-like nanotubes are in the range of 3.6–4.0 nm, while their outer diameters are in the range of 7.6–8 nm. In addition, some straight nanotubes form bundles which are hundreds of nanometers in length. As-synthesized ultrathin nanotubes and crystalline precursors were evaluated by methyl orange dye (MOD) UV photo-oxidation. The complete degradation of MOD is achieved after 3.5 h of UV irradiation in the presence of silver–TiO2 nanocomposites, resulting in 50% of dye mineralization.

February, 2012 | DOI: 10.1016/j.molcata.2011.11.020

Title: Hydrogenation of 2,2,2-trifluoroacetophenone: Molecular insight into the role of solvent in enantioselection
Author(s): Rosa Pereñiguez; Gianluca Santarossa; Tamas Mallat; Alfons Baiker
Source: Journal of Molecular Catalysis A: Chemical, 365 (2012) 39-49

abstract | fulltext

The unique solvent effect in the enantioselective hydrogenation of α-fluorinated ketones has been investigated in ten different solvents using the  hydrogenation of 2,2,2-trifluoroacetophenone (1) on cinchonine (CN)-modified Pt/Al2O3 as a model reaction. Application of strongly basic solvents – but also increasing hydrogen pressure or conversion – inverted the sense of enantiodifferentiation from (S)-alcohol (expected enantiomer based on the stereochemistry of CN) to (R)-alcohol. The known formation of hemiketals was the origin of the inversion in alcohols. Considering only the non-reacting solvents and low conversions at low pressures, the best correlation was established between the enantiomeric excess and the solvent basicity represented by the H-bond acceptor ability (β). In contrast to former proposals, solvent acidity (α) did not play a significant role. The experimental results are validated by theoretical calculations. The docking of 1 to CN has been investigated in the absence of solvent and also in the presence of toluene and dimethyl formamide. Several competing docking complexes have been isolated that can coexist on the metal surface. Detailed analyses of these complexes show that their stabilities depend on the formation of enantiospecific local interactions between 1, CN, and the platinum surface. The presence of solvent interferes with these interactions, affecting the relative stability of the docking complexes. A correlation between the solvent-induced interactions at molecular level and changes in enantioselectivity is suggested.

December, 2012 | DOI: 10.1016/j.molcata.2012.08.006

Title: Roughness assessment and wetting behavior of fluorocarbon surfaces
Author(s): Terriza, A; Alvarez, R; Borras, A; Cotrino, J; Yubero, F; Gonzalez-Elipe, AR
Source: Journal of Colloid and Interface Science, 376 (2012) 274-282

abstract | fulltext

The wetting behavior of fluorocarbon materials has been studied with the aim of assessing the influence of the surface chemical composition and surface roughness on the water advancing and receding contact angles. Diamond like carbon and two fluorocarbon materials with different fluorine content have been prepared by plasma enhanced chemical vapor deposition and characterized by X-ray photoemission, Raman and FT-IR spectroscopies. Very rough surfaces have been obtained by deposition of thin films of these materials on polymer substrates previously subjected to plasma etching to increase their roughness. A direct correlation has been found between roughness and water contact angles while a superhydrophobic behavior (i.e., water contact angles higher than 150° and relatively low adhesion energy) was found for the films with the highest fluorine content deposited on very rough substrates. A critical evaluation of the methods currently used to assess the roughness of these surfaces by atomic force microscopy (AFM) has evidenced that calculated RMS roughness values and actual surface areas are quite dependent on both the scale of observation and image resolution. A critical discussion is carried out about the application of the Wenzel model to account for the wetting behavior of this type of surfaces.

June, 2012 | DOI: 10.1016/j.jcis.2012.03.010

Title: Remediation of metal-contaminated soils with the addition of materials - Part II: Leaching tests to evaluate the efficiency of materials in the remediation of contaminated soils
Author(s): Gonzalez-Nunez, R; Alba, MD; Orta, MM; Vidal, M; Rigol, A
Source: Chemosphere, 87 (2012) 829-837

abstract | fulltext

The effect of the addition of materials on the leaching pattern of As and metals (Cu, Zn, Ni, Pb, and Cd) in two contaminated soils was investigated. The examined materials included bentonites, silicates and industrial wastes, such as sugar foam, fly ashes and a material originated from the zeolitization of fly ash. Soil + material mixtures were prepared at 10% doses. Changes in the acid neutralization capacity, crystalline phases and contaminant leaching over a wide range of pHs were examined by using pHstat leaching tests. Sugar foam, the zeolitic material and MX-80 bentonite produced the greatest decrease in the leaching of pollutants due to an increase in the pH and/or the sorption capacity in the resulting mixture. This finding suggests that soil remediation may be a feasible option for the reuse of non-hazardous wastes.

May, 2012 | DOI: 10.1016/j.chemosphere.2012.01.015

Title: Preferential oxidation of CO (CO-PROX) over CuOx/CeO2 coated microchannel reactor
Author(s): Laguna, OH; Ngassa, EM; Oraa, S; Alvarez, A; Dominguez, MI; Romero-Sarria, F; Arzamendi, G; Gandia, LM; Centeno, MA; Odriozola, JA
Source: Catalysis Today, 180 (2012) 105-110

abstract | fulltext

The general aspects of the synthesis and characterization results of a CuO x/CeO 2 catalyst were presented. In addition the principal steps for manufacturing a microchannel reactor and for the coating of the CuO x/CeO 2 catalyst onto the microchannels walls, were also summarized. The catalytic activity of this microchannel reactor during the preferential oxidation of CO (CO-PROX) was evaluated employing a feed-stream that simulates a reformate off-gas after the WGS unit. Two activation atmospheres were studied (H 2/N 2 and O 2/N 2). The reducing pretreatment improved the resistance to deactivation by formation of carbonaceous species over the catalyst surface at high temperatures. The presence of H 2O and CO 2 in the feed-stream was also analyzed indicating that the adsorption of CO 2 inhibited the conversion of CO at lower temperatures because these compounds modified the active sites through the formation of carbonaceous species on the catalyst surface. Finally, the experimental results of the microreactor performance were compared with CFD simulations that were carried out using a kinetic for the CuO x/CeO 2 powder catalyst. The experimental results were reasonably well described by the model, thus confirming its validity.

January, 2012 | DOI: 10.1016/j.cattod.2011.03.024

Title: Analysis and application of the theories that rationalize the crystalline structures of fluorite-related rare earth oxides
Author(s): Lopez-Cartes, C; Perez-Omil, JA; Rodriguez-Izquierdo, JM; Calvino, JJ
Source: Catalysis Today, 180 (2012) 161-180

abstract | fulltext

The main current theories dealing with the crystalline structures of the fluorite related rare earth oxides, including those corresponding to reduced oxides, one based on the distribution of the coordination defect inside the fluorite structure, and the other which proposes the establishment of modular sequences constituted by modules with fluorite structure, are presented and comparatively explored in detail. Our in-depth analysis of both approximations indicates that they in fact provide smart and efficient rationalizations of the currently known intermediate rare earth oxides structures. We prove however that the strict application of the principles and rules proposed by each theory does not yield unique and unambiguous results for most of the members of the homologous series, as it has been claimed up to now. Moreover, the controversy about the reliability of these two, apparently different and competing, theories is definitely clarified and the exact equivalence of their structural predictions is demonstrated. Finally, we propose new extra systematization rules, not considered up to now in neither of these theoretical approaches, to overcome the observed limitations to properly rationalize the structure of this so technologically important family of oxides.

January, 2012 | DOI: 10.1016/j.cattod.2011.04.032

Title: Ethanol partial photoxidation on Pt/TiO2 catalysts as green route for acetaldehyde synthesis
Author(s): Murcia, JJ; Hidalgo, MC; Navio, JA; Vaiano, V; Ciambelli, P; Sannino, D
Source: Catalysis Today, 196 (2012) 101-109

abstract | fulltext

Heterogeneous photocatalytic partial oxidation of ethanol was studied over different Pt/TiO2 as an alternative green process for acetaldehyde production.

The catalysts were synthesized through the photodeposition of Pt over sol–gel TiO2 with platinum loads of 0.5 and 1 wt.%. The effect of some experimental conditions during photodeposition, such as deposition time and Pt loading, was investigated. A short deposition time at 0.5 wt.% Pt nominal loading led to small average particle size of platinum (2–3 nm) homogeneously distributed all over the TiO2 surface.

Ethanol partial oxidation was tested in a gas–solid photocatalytic fluidized bed reactor at high illumination efficiency, using different reaction temperatures. Activity results have been correlated with characterization results of the different samples. Platinized samples prepared with short deposition times showed high conversion levels and high selectivity to acetaldehyde. Materials prepared at longer times, 120 min, showed selectivities >98%, although with lower ethanol conversion.

Sample with 1 wt.% Pt loading prepared with 15 min deposition time combined a good compromise between a relevant ethanol conversion and a very high selectivity to acetaldehyde at a selected reaction temperature of 80 °C, with an acetaldehyde yield higher than 80%, which make of this catalyst a good candidate for acetaldehyde production by photocatalysis.

November, 2012 | DOI: 10.1016/j.cattod.2012.02.033

Title: Redox and catalytic properties of CuO/CeO2 under CO + O2 + NO: Promoting effect of NO on CO oxidation
Author(s): Martinez-Arias, A.; Hungria, A. B.; Iglesias-Juez, A.; Fernandez-Garcia, M.; Anderson, J. A.; Conesa, J. C.; Munuera, G.; Soria, J.
Source: Catalysis Today, 180 (2012) 81-87

abstract | fulltext

A CuO/CeO2 catalyst has been studied with respect to its catalytic activity for CO oxidation under stoichiometric conditions employing either O2 or O2–NO mixture as oxidants. The obtained results are rationalised on the basis of analysis of redox properties upon interaction with CO and O2–NO by EPR as well as by redox/catalytic analysis by operando-DRIFTS. These provide useful insight into the processes involved during NO reduction, for which two well differentiated steps associated to a change in the type of active centres during the course of the reaction are evidenced. Nevertheless, the most interesting result is related to observation of a novel promoting effect of NO on CO oxidation. This is explained mainly on the basis of DRIFTS results and appears to be associated with phenomena of adsorption/desorption of NOx species at interfacial positions which apparently activate such interfacial region allowing formation of greater amounts of active reduced copper centres in the presence of NO.

January, 2012 | DOI: 10.1016/j.cattod.2011.02.014

Title: DRIFTS study of methanol adsorption on Mg-Al hydrotalcite catalysts for the transesterification of vegetable oils
Author(s): Navajas, A; Arzamendi, G; Romero-Sarria, F; Centeno, MA; Odriozola, JA; Gandia, LM
Source: Catalysis Communications, 7 (2012) 189-193

abstract | fulltext

Mg-Al hydrotalcites rehydrated after calcination are promising catalysts for the methanolysis of vegetable oils. To gain insight into the basis of their catalytic action, the adsorption of methanol over some commercial Mg-Al hydrotalcites was studied by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Different species formed after methanol adsorption were identified, being the total quantity of methoxy species related to the basic character of the sample. A linear correlation between the amount of adsorbed monodentate methoxy species and the catalytic activity in the biodiesel production was found. Therefore, it is proposed that these species are the mainly involved in the transesterification reaction.

January, 2012 | DOI: 10.1016/j.catcom.2011.11.005

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