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Artículos SCI



2009


Aluminium anodisation for Au-CeO2/Al2O3-Al monoliths preparation


Sanz, O; Martinez, LM; Echave, FJ; Dominguez, MI; Centeno, MA; Odriozola, JA; Montes, M
Chemical Engineering Journal, 151 (2009) 324-332

ABSTRACT

The anodisation of aluminium monoliths was performed in order to generate an alumina layer that ensures a good adherence of the catalysts. In this study, it is demonstrated that the morphology of the produced alumina layer depends on time, temperature, current density and concentration of the selected electrolyte. When anodisation process with the extreme conditions was applied (30 °C, 50 min, 2 A dm−2 and 2.6 M of sulphuric acid) a significant cracks were obtained and used to fix the subsequent catalytic coatings. The washcoating method was used to cover the monoliths with colloidal solutions of CeO2 and/or Au-CeO2 catalysts. The resulting monolithic catalysts were tested in the CO oxidation reaction being 1%Au-CeO2 containing system the most active. The structured catalyst prepared this way changed neither the textural nor the catalytic properties of the deposited catalytic powders.


Agosto, 2009 | DOI: 10.1016/j.cej.2009.03.062

Influence of sulfur on the structural, surface properties and photocatalytic activity of sulfated TiO2


Colon, G; Hidalgo, MC; Navio, JA; Kubacka, A; Fernandez-Garcia, M
Applied Catalysis B-Environmental, 90 (2009) 633-641

ABSTRACT

TiO2 materials were prepared by sol–gel method and then impregnated with sulfuric acid and calcined using different temperatures and atmosphere (air and nitrogen). Systematic variation of these two experimental parameters makes possible to modulate the amount of surface sulfur from the impregnation procedure. The best photocatalyst for liquid phenol degradation was obtained after calcination at 700 °C in air, while gas toluene degradation optimum performance is obtained by calcination at 700 °C in nitrogen from 500 °C. Structural analysis of these materials by XRD, micro-Raman spectroscopy and FE-SEM shows that once calcined at 700 °C the material was a well-crystallized, high surface area anatase structure in all cases. The surface characterization by FTIR and XPS confirms the presence of a higher amount of sulfur species and acidic OH groups in samples partially calcined in nitrogen, and a low XPS O/Ti-atomic ratio with the O 1s peak shifted to higher binding energies (1.8 vs. 2 ± 0.1 and 530.4 eV vs. 529.8 eV, respectively, against the reference materials) for samples calcined at 700 °C, temperature at which most of sulfate species have been evolved. The paper presents an attempt to correlate the contribution of the observed structural defects within the anatase sub-surface layers and surface acidity to the different photoactivity behaviour exhibited for phenol liquid phase and toluene gas phase photodegradation.


Agosto, 2009 | DOI: 10.1016/j.apcatb.2009.04.026

Mineralogical stability of phyllosilicates in hyperalkaline fluids: Influence of layer nature, octahedral occupation and presence of tetrahedral Al


Becerro, AI; Mantovani, M; Escudero, A
American Mineralogist, 94 (2009) 1187-1197

ABSTRACT

Mineralogical changes in a set of phyllosilicates, differing in their layer nature, chemical composition, octahedral character, and Al content of the tetrahedral sheet, were analyzed after hydrothermal reaction in an alkaline solution. The composition of the alkaline solution was selected to simulate the first stage of cement degradation [NaOH-KOH-Ca(OH)2]. The reaction products have been analyzed by XRD, 29Si and 27Al MAS NMR spectroscopy, SEM/EDX, and TEM. The results indicate that the main factor influencing the stability of the clays is the occupation of the octahedral sheet such that all trioctahedral members withstand the alkaline attack, whereas most of the dioctahedral clays suffer a complete dissolution and crystallization of new phases. Second, clays with Al in the tetrahedral sheet of their layers are shown to be less stable than those with a pure Si tetrahedral sheet.


Agosto, 2009 | DOI: 10.2138/am.2009.3164

Kinetics of the thermal decomposition of anhydrous cobalt nitrate by SCRT method


Ortega, A; Macias, M; Gotor, FJ
Journal of Thermal Analysis and Calorimetry, 98 (2009) 441-448

ABSTRACT

It has been shown the ability of the Sample Controlled Reaction Temperature (SCRT) method for both discriminate the kinetic law and calculate the activation energy of the reaction. This thermal decomposition is best described by a Johnson–Mehl–Avrami kinetic model (with n = 2) with an activation energy of nuclei growth which fall in the range 52–59 kJ mol−1. The process is not a single-step because the initial rate of decomposition is likely to be limited by nucleation. The results reported here constitute the first attempt to use the new SCRT method to study the kinetic of the thermal decomposition of cobalt nitrate.


Agosto, 2009 | DOI: 10.1007/s10973-009-0322-y

Near-ambient X-ray photoemission spectroscopy and kinetic approach to the mechanism of carbon monoxide oxidation over lanthanum substituted cobaltites


Hueso, JL; Martinez-Martinez, D; Caballero, A; Gonzalez-Elipe, AR; Mun, BS; Salmeron, M
Catalysis Communications, 10 (2009) 1898-1902

ABSTRACT

We have studied the oxidation of carbon monoxide over a lanthanum substituted perovskite (La0.5Sr0.5CoO3−d) catalyst prepared by spray pyrolysis. Under the assumption of a first-order kinetics mechanism for CO, it has been found that the activation energy barrier of the reaction changes from ∼80 to ∼40 kJ mol−1 at a threshold temperature of ca. 320 °C. In situ XPS near-ambient pressure (∼0.2 torr) shows that the gas phase oxygen concentration over the sample decreases sharply at ca. 300 °C. These two observations suggest that the oxidation of CO undergoes a change of mechanism at temperatures higher than 300 °C.


Agosto, 2009 | DOI: 10.1016/j.catcom.2009.06.022

Reactivity of LaNi1−y Co y O3−δ Perovskite Systems in the Deep Oxidation of Toluene


Pereniguez, R; Hueso, JL; Holgado, JP; Gaillard, F; Caballero, A
Catalysis Letters, 131 (2009) 164-169

ABSTRACT

In the present work we have evaluated the oxidation of toluene over different lanthanum perovskites with a general composition of LaNi1−y Co y O3−δ. These catalysts, prepared by a spray pyrolysis method, have been characterised by XRD, BET and FE-SEM techniques. Additional experiments of temperature programmed desorption of O2, reduction in H2 and X-ray absorption spectroscopy were also performed in order to identify the main surface oxygen species and the reducibility of the different perovskites. The catalytic behaviour toward the oxidation of toluene (as a model for VOCs compounds) was evaluated in the range 100–600 °C, detecting a total conversion for all the samples below 400 °C and higher activities for the cobalt-containing perovskites. The catalytic behaviour of these samples is consistent with a suprafacial mechanism, with the α-type oxygen playing an active role in the oxidation reaction.


Agosto, 2009 | DOI: 10.1007/s10562-009-9968-0

Comparative investigation of TiAlC(N), TiCrAlC(N), and CrAlC(N) coatings deposited by sputtering of МАХ-phase Ti2 − хCrхAlC targets


Shtansky, DV; Kiryukhantsev-Korneev, PV; Sheveyko, AN; Mavrin, BN; Rojas, C; Fernandez, A; Levashov, EA
Surface and Coatings Technology, 203 (2009) 3595-3609

ABSTRACT

A comparative investigation of the structure and properties of TiAlC(N), TiCrAlC(N), and CrAlC(N) coatings deposited by sputtering of МАХ-phase Ti2 − хCrхAlC targets (where x = 0, 0.5, 1.5, and 2) in an Ar atmosphere or in a gaseous mixture of Ar + N2 is presented. The coatings were characterized in terms of their structure, elemental and phase composition, hardness, elastic modulus, elastic recovery, thermal stability, friction coefficient, wear rate, corrosion, and high-temperature oxidation resistance. The structure of the coatings was studied by means of X-ray diffraction, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy, glow discharge optical emission spectroscopy, electron energy loss spectroscopy, and Raman spectroscopy. To evaluate the thermal stability and oxidation resistance, the coatings were annealed either in vacuum or in air at temperatures 600–1200 °C. The results obtained show that the TiAlCN coatings possess high hardness of 32–35 GPa, low friction coefficient against WC–Co well below 0.25, high thermal stability up to 1200 °C, and superior performance in dry milling tests against high Cr steel. Meanwhile, the coatings with high Cr content demonstrated improved oxidation resistance up to 1000 °C and superior electrochemical behavior, but their mechanical and tribological properties were deteriorated.


Agosto, 2009 | DOI: 10.1016/j.surfcoat.2009.05.036

Structural characteristics and morphology of SmxCe1−xO2−x/2 thin films


Hartmanova, M; Jergel, M; Mansilla, C; Holgado, JP; Zemek, J; Jurek, K; Kundracik, F
Applied Surface Science, 255 (2009) 9085-9091

ABSTRACT

Effect of the deposition temperature (200 and 500 °C) and composition of SmxCe1−xO2−x/2 (x = 0, 10.9–15.9 mol%) thin films prepared by electron beam physical vapor deposition (EB-PVD) and Ar+ ion beam assisted deposition (IBAD) combined with EB-PVD on structural characteristics and morphology/microstructure was investigated. The X-ray photoelectron spectroscopy (XPS) of the surface and electron probe microanalysis (EPMA) of the bulk of the film revealed the dominant occurrence of Ce4+ oxidation state, suggesting the presence of CeO2 phase, which was confirmed by X-ray diffraction (XRD). The Ce3+ oxidation states corresponding to Ce2O3 phase were in minority. The XRD and scanning electron microscopy (SEM) showed the polycrystalline columnar structure and a rooftop morphology of the surface. Effects of the preparation conditions (temperature, composition, IBAD) on the lattice parameter, grain size, perfection of the columnar growth and its impact on the surface morphology are analyzed and discussed.


Agosto, 2009 | DOI: 10.1016/j.apsusc.2009.06.108

Chemical and electronic interface structure of spray pyrolysis deposited undoped and Al-doped ZnO thin films on a commercial Cz-Si solar cell substrate


Gabas, M; Barrett, NT; Ramos-Barrado, JR; Gota, S; Rojas, TC; Lopez-Escalante, MC
Solar Energy Materials and Solar Cells, 93 (2009) 1356-1365

ABSTRACT

We have studied differences in the interface between undoped and Al-doped ZnO thin films deposited on commercial Si solar cell substrates. The undoped ZnO film is significantly thicker than the Al-doped film for the same deposition time. An extended silicate-like interface is present in both samples. Transmission electron microscopy (TEM) and photoelectron spectroscopy (PES) probe the presence of a zinc silicate and several Si oxides in both cases. Although Al doping improves the conductivity of ZnO, we present evidence for Al segregation at the interface during deposition on the Si substrate and suggest the presence of considerable fixed charge near the oxidized Si interface layer. The induced distortion in the valence band, compared to that of undoped ZnO, could be responsible for considerable reduction in the solar cell performance.


Agosto, 2009 | DOI: 10.1016/j.solmat.2009.02.018

Synthesis of complex carbonitride powders TiyMT1−yCxN1−x (MT: Zr, V, Ta, Hf) via a mechanically induced self-sustaining reaction


Cordoba, JM; Aviles, MA; Sayagues, MJ; Alcala, MD; Gotor, FJ
Journal of Alloys and Compounds, 482 (2012) 349-355

ABSTRACT

The machinability of materials is a dynamic field with enormous implications in different industrial sectors because manufacturers are constantly looking for improvements that can increase the overall productivity. Manufacturers of cutting tool inserts need to develop products that can perform at higher speeds and last longer under increasingly rigorous operating conditions. It has been revealed that cermets may exhibit better properties and performances when solid solution of multiple hard compounds is added instead of a mixture of several binary ones. In this work, a mechanically induced self-sustaining reaction (MSR) is described as a suitable synthesis method to obtain a wide range of different new quaternary carbonitride systems by milling mixtures of elemental powders of transition metals and graphite in a nitrogen atmosphere. Characterization was carried out using X-ray powder diffraction, elemental analysis, energy dispersive X-ray analysis (EDX), scanning and transmission electron microscopy and electron diffraction (ED).


Agosto, 2009 | DOI: 10.1016/j.jallcom.2009.04.012

Incorporation and Thermal Evolution of Rhodamine 6G Dye Molecules Adsorbed in Porous Columnar Optical SiO2 Thin Films


Sanchez-Valencia, JR; Blaszczyk-Lezak, I; Espinos, JP; Hamad, S; Gonzalez-Elipe, AR; Barranco, A
Langmuir, 25 (2009) 6869-6874

ABSTRACT

Rhodamine 6G (Rh6G) dye molecules have been incorporated into transparent and porous SiO2 thin films prepared by evaporation at glancing angles. The porosity of these films has been assessed by analyzing their water adsorption isotherms measured for the films deposited on a quartz crystal monitor. Composite Rh6G/SiO2 thin films were prepared by immersion of a SiO2 thin film into a solution of the dye at a given pH. It is found that the amount of Rh6G molecules incorporated into the film is directly dependent on the pH of the solution and can be accounted for by a model based on the point of zero charge (PZC) concepts originally developed for colloidal oxides. At low pHs, the dye molecules incorporate in the form of monomers, while dimers or higher aggregates are formed if the pH increases. Depending on the actual preparation and treatment conditions, they also exhibit high relative fluorescence efficiency. The thermal stability of the composite films has been also investigated by characterizing their optical behavior after heating in an Ar atmosphere at increasing temperatures up to 275 °C. Heating induces a progressive loss of active dye molecules, a change in their agglomeration state, and an increment in their relative fluorescence efficiency. The obtained Rh6G/SiO2 composite thin films did not disperse the light and therefore can be used for integration into optical and photonic devices.


Agosto, 2009 | DOI: 10.1021/la900695t

Identification of hydrogen and deuterium at the surface of water ice by reflection electron energy loss spectroscopy


Yubero, F; Tokesi, K
Applied Physics Letters, 95 (2009) 084101

ABSTRACT

A nondestructive method to distinguish between hydrogen (H) and deuterium (D) at surfaces by reflection electron energy loss spectroscopy is presented. It is based on the analysis of the energy distributions of electrons elastically backscattered from surfaces containing H or D. We consider standard and deuterated water ices as test surfaces. The recoil energy of the backscattered electrons depends on the atomic mass of the targets, and the contributions of H, D, and O to the measured spectra can be easily separated. The results of Monte Carlo simulations corroborate the experimental findings.


Agosto, 2009 | DOI: 10.1063/1.3202402

Light generation at the anomalous dispersion high energy range of a nonlinear opal film


Botey, M; Maymo, M; Molinos-Gomez, A; Dorado, L; Depine, RA; Lozano, G; Mihi, A; Miguez, H; Martorell, J
Optics Express, 17 (2009) 12210-12216

ABSTRACT

We study experimentally and theoretically light propagation and generation at the high energy range of a close-packed fcc photonic crystal of polystyrene spheres coated with a nonlinear material. We observe an enhancement of the second harmonic generation of light that may be explained on the basis of amplification effects arising from propagation at anomalous group velocities. Theoretical calculations are performed to support this assumption. The vector KKR method we use allows us to determine, from the linear response of the crystal, the behavior of the group velocity in our finite photonic structures when losses introduced by absorption or scattering by defects are taken into account assuming a nonzero imaginary part for the dielectric constant. In such structures, we predict large variations of the group velocity for wavelengths on the order or smaller than the lattice constant of the structure, where an anomalous group velocity behavior is associated with the flat bands of the photonic band structure. We find that a direct relation may be established between the group velocity reduction and the enhancement of a light generation processes such as the second harmonic generation we consider. However, frequencies for which the enhancement is found, in the finite photonic crystals we use, do not necessarily coincide with the frequencies of flat high energy bands.


Julio, 2009 | DOI: 10.1364/OE.17.012210

A recurrent error which needs to be resolved


Ortega, A
Thermochimica Acta, 491 (2009) 116-117

ABSTRACT

The recent paper by Jankovic et al. [B. Janković, B. Adnađevic, J. Jovanović; Thermochimica Acta 452 (2007) 106] and other similar papers have raised a problem which needs to be resolved. These authors use the method of Kennedy and Clark [J.A. Kennedy, S.M. Clark, Thermochimica Acta 307 (1997) 27] which is conceptually erroneous; this is analyzed in this paper.


Julio, 2009 | DOI: 10.1016/j.tca.2009.02.009

Deposition of Al-Fe pillared bentonites and gold supported Al-Fe pillared bentonites on metallic monoliths for catalytic oxidation reactions


Martinez, LM; Dominguez, MI; Sanabria, N; Hernandez, WY; Moreno, S; Molina, R; Odriozola, JA; Centeno, MA
Applied Catalysis A-General, 364 (2009) 166-173

ABSTRACT

Al-Fe pillared bentonite and gold supported on Al-Fe pillared bentonite catalysts deposed on Fecralloy monoliths have been prepared, characterized and tested in two oxidation reactions: gaseous oxidation of CO and phenol oxidation in aqueous medium. The deposition of the solid on the metallic substrate does not alter its structural characteristics. The use of monoliths improves the activity in both reactions and offers the additional advantage to facilitate the separation of the catalyst from the reaction medium.


Julio, 2009 | DOI: 10.1016/j.apcata.2009.05.046

Effect of Sulfate Pretreatment on Gold-Modified TiO2 for Photocatalytic Applications


Hidalgo, MC; Maicu, M; Navio, JA; Colon, G
Journal of Physical Chemistry C, 113 (2009) 12840-12847

ABSTRACT

The influence of sulfated pretreatment of TiO2 on the structure, morphology, and dispersion of gold and photocatalytic properties of Au/TiO2 were studied. Notable enhancements in the photocatalytic activity of TiO2 were achieved by deposition of gold onto samples that had previously undergone sulfate treatment followed by high temperature calcination. The enhancement in activity can be attributed to the stronger bonding and improved electronic communication between gold particles and TiO2 on defect rich surfaces as are found on sulfated samples after calcination at 700 °C. Two different methods for gold deposition were evaluated: chemical reduction by citrate and photodeposition. The citrate method produced more homogeneous and smaller gold particles with a better dispersion than photodeposition, which lead to greater increases in activity in the photocatalytic degradation of phenol when the former method was used for deposition on both sulfated and nonsulfated TiO2. The combination of sulfate pretreatment and gold deposition by chemical reduction was shown to be a good strategy to obtain gold/titania catalysts possessing homogeneous particle size and dispersion of the metal and a strong bonding between the Au and the TiO2 surface.


Julio, 2009 | DOI: 10.1021/jp903432p

Electrical characteristics of mixed Zr–Si oxide thin films prepared by ion beam induced chemical vapor deposition at room temperature


Ferrer, FJ; Frutos, F; Garcia-Lopez, J; Jimenez, C; Yubero, F
Thin Solid Films, 517 (2009) 5446-5452

ABSTRACT

Mixed Zr–Si oxide thin films have been prepared at room temperature by ion beam decomposition of organometallic volatile precursors. The films were flat and amorphous. They did not present phase segregation of the pure single oxides. A significant amount of impurities (–C–, –CHx, –OH, and other radicals coming from partially decomposed precursors) remained incorporated in the films after the deposition process. This effect is minimized if the Ar content in the O2/Ar bombarding gas is maximized. Static permittivity and breakdown electrical field of the films were determined by capacitance–voltage and current–voltage electrical measurements. It is found that the static permittivity increases non-linearly from ~ 4 for pure SiO2 to ~ 15 for pure ZrO2. Most of the dielectric failures in the films were due to extrinsic breakdown failures. The maximum breakdown electrical field decreases from ~ 10.5 MV/cm for pure SiO2 to ~ 45 MV/cm for pure ZrO2. These characteristics are justified by high impurity content of the thin films. In addition, the analysis of the conduction mechanisms in the formed dielectrics is consistent to Schottky and Poole-Frenkel emission for low and high electric fields applied, respectively.


Julio, 2009 | DOI: 10.1016/j.tsf.2009.01.099

ZnO activation by using activated carbon as a support: Characterisation and photoreactivity


Melian, EP; Diaz, OG; Rodriguez, JMD; Colon, G; Arana, J; Melian, JH; Navio, JA; Pena, JP
Applied Catalysis A-General, 364 (2009) 176-181

ABSTRACT

The effect of the mixing ZnO with different portions of activated carbon (AC) has been studied. The resulting catalysts were characterised and evaluated in the photocatalytic decomposition of aqueous pollutants. Changes in the catalyst colour and in the FTIR vibration bands of the surface hydroxyl groups were recorded. νOH vibrations were shifted to lower wavenumbers as AC loading increased, demonstrating modification of the acid-base character of the catalysts. Laser scattering studies showed that AC loading leads to smaller ZnO particles. BET surface area measurements and scanning electron micrograph (SEM) analysis showed agglomeration of ZnO particle pores in the AC structure.

Results showed that in addition to a synergistic effect of the AC-ZnO combination, AC content modifies the ZnO particle properties and consequently photocatalytic behaviour. This was evident in phenol degradation experiments where changes in the concentration profiles of the catechol and hydroquinone degradation intermediates, were observed. However, the AC-ZnO catalysts were less efficient than pure ZnO in the degradation of 2,4-dichlorophenol (DCP). This seems to be due to the strong adsorption of the DCP molecule on AC, resulting in lower diffusion to the catalytic ZnO and thus a lower rate of photocatalysis.


Julio, 2009 | DOI: 10.1016/j.apcata.2009.05.042

Nanoindentation of TiO2 thin films with different microstructures


Gaillard, Y; Rico, VJ; Jimenez-Pique, E; Gonzalez-Elipe, AR
Journal of Physics D: Applied Physics, 42 (2009) 145305

ABSTRACT

A series of nanoindentation tests has been carried out with TiO2 films produced by physical vapour deposition (PVD) under different conditions. Films with different microstructures and crystallographic structures have been prepared by changing experimental parameters such as the temperature of the substrate, the deposition angle (by the so-called glancing angle physical vapour deposition, GAPVD) or by exposing the growing film to a beam of accelerated ions. The obtained results of hardness and Young's modulus depict interesting correlations with the microstructure and structure of the films providing a general picture for the relationships between these characteristics and their mechanical properties. Different models have been used to extract Young's modulus and hardness parameters from the experimental nanoindentation curves. The obtained results are critically discussed to ascertain the ranges of validity of each procedure according to the type of sample investigated.


Julio, 2009 | DOI: 10.1088/0022-3727/42/14/145305

Degradation of n-Butyl tin Chlorides in Waters. A Comparative Assessment of the Process by Photo-assisted and Chemical- treatment Methods


Navio, JA; Cerrillos, C; Macias, M
Journal of Advanced Oxidation Technologies, 12 (2009) 158-163

ABSTRACT

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