A theoretical insight into the catalytic effect of a mixed-metal oxide at the nanometer level: The case of the highly active metal/CeOx/TiO2(110) catalysts

The structural and electronic properties of CeOx species supported on the rutile TiO2 110 surface have been examined by means of periodic density-functional calculations that use a generalized gradient approximation functional including a Hubbard-like type correction. Deposition of Ce atoms leads in a first step to Ce3+ ions bound to the surface through bridge and in-plane oxygen atoms, the released electrons occupying the Ti 3d empty orbitals. Further addition of Ce and molecular oxygen gives place to Ce2O3 dimers diagonally arranged on the surface, in agreement with the spots observed in the scanning tunnel microscope images. The formation process of CeOx nanoparticles NPs on the TiO2 surface is highly exothermic and our calculations show that the redox properties of the Ce III-Ce IV couple are significantly altered when it is supported on TiO2. In particular the reactivity against CO/O2 indicates that on the surface the presence of Ce III is favored over Ce IV species. Our results also indicate that the CeOx /TiO2 interface should be seen like a real mixed-metal oxide rather than a supported NP of ceria. Finally, in the context of the high catalytic activity of the M /CeOx /TiO2 M =Au,Cu,Pt systems in the water-gas shift reaction, we have examined the dissociation of water on the CeOx /TiO2 surface and estimated a barrier as small as 0.04 eV, i.e. 8 times smaller than that computed for a TiO2 oxygen vacancy. This result agrees with the experimental superior catalytic activity of the M /CeOx /TiO2 systems over M /TiO2.Gobierno de España. Ministerio Ciencia e Innovación (MICINN) MAT2005-01872 y CSD2008-0023Junta de Andalucía FQM-132Departamento de Energía de EE. UU. División de Subvención de Ciencias Químicas DE-AC02-98CH1088

Interaction of oxygen with TiN (001): N↔O exchange and oxidation process

This work presents a detailed experimental and theoretical study of the oxidation of TiN(001) using a combination of synchrotron-based photoemission and density functional theory (DFT). Experimentally, the adsorption of O2 on TiN(001) was investigated at temperatures between 250 and 450K. At the lowest temperature, there was chemisorption of oxygen (O2,gas→2Oads) without significant surface oxidation. In contrast, at 450K the amount of O2 adsorbed increased continuously, there was no evidence for an oxygen saturation coverage, a clear signal in the Ti 2p core level spectra denoted the presence of TiOx species, and desorption of both N2 and NO was detected. The DFT calculations show that the adsorption/dissociation of O2 is highly exothermic on a TiN(001) substrate and is carried out mainly by the Ti centers. A high oxygen coverage (larger than 0.5 ML) may induce some structural reconstructions of the surface. The exchange of a surface N atom by an O adatom is a highly endothermic process (ΔE=2.84eV). However, the overall oxidation of the surface layer is thermodynamically favored due to the energy released by the dissociative adsorption of O2 and the formation of N2 or NO. Both experimental and theoretical results lead to conclude that a TiN+mO2→TiOx+NO reaction is an important exit channel for nitrogen in the oxidation process.Ministerio de Educación y Ciencia de España, MEC. MAT2005-01872Junta de Andalucía. FQM-132División de Ciencias Químicas del Departamento de Energía de EE. UU. DE-AC02-98CH10086Fundación japonesa para la Ciencia de los Materiale

Personal aircraft: a more affordable luxury

Access to luxury products has been limited traditionally to the upper classes. Products and services related to the means of transport have usually been considered of luxury and industrialization has made accessible to much of the population in developed countries. An emerging market is personal aircraft which is currently restricted to certain layers of society but it is expected that their use will represent the next great advance in transport. This article has the object of presenting the results of ongoing research and it focuses on possible demand and the tendency to use this transport option in Spanish societ

Trees, homology, and automorphism groups of RAAGs

We study the homology of an explicit finite-index subgroup of the automorphism group of a partially commutative group, in the case when its defining graph is a tree. More concretely, we give a lower bound on the first Betti number of this subgroup, based on the number and degree of a certain type of vertices, which we call deep. We then use combinatorial methods to analyze the average value of this Betti number, in terms of the size of the defining tree

Outsourcing en la Indústria de Fabricantes de Vehículos en España: Evolución, Tendencias, Causas y Consecuencias.

Winds as an environmental factor can cause significant difficulties for the railway system operation. The rail way overhead has been particularly vulnerable to cross-winds related problems, such as development of und amped oscillations due to galloping phenomenon. The installation of windbreaks to decrease the aerodynamic loads on the train can affect the loads on railway overheads triggering cable galloping. One essential parameter to indicate the influence of the parapet wake on the catenary contact wire is the turbulence intensity. In this paper the results of an experimental analysis of the turbulence intensity due to the presence of parapets carried out in a wind tunnel are reported. Embankments equipped with different parapets have been tested and turbulence intensity has been measured at both contact wire locations, windward and leeward. The relative influence of the parapets is measured through a reduced turbulence intensity, defined as the ratio between the turbulence intensity measured with parapet and the turbulence intensity in the case without any parapet on the embankment. In general the reduced turbulence intensity increases as the height of the parapet increases

Propuesta de un Modelo para la Gestión de los Neumáticos de Una flota de Vehículos

En la gestión de los neumáticos de una flota de vehículos el mejor ratio para ello es el coste del neumático dividido por las Horas o Km. realizados por el neumático, pero existen flotas de vehículos que por sus características de uso no se puede realizar un seguimiento de las horas o Km. que realiza el neumático en su vida útil ya que son vehículos que son utilizados por un gran número de conductores en diferentes turnos al día. Este tipo de flotas suelen operar en entornos urbanos y son: Vehículos destinados a la limpieza viaria, recogida de basuras, mantenimiento de jardines, Policía, Guardia Civil, Bomberos etc. así también en menor medida flotas de empresas, renting de vehículos, alquiler de vehículos etc. por ello se propone un modelo de gestión de neumáticos para una flota de vehículos en los que no se puede hacer un seguimiento de las horas o kilómetros realizados por el neumático en su uso

Origen de la radiodifusión pirata comercial

La importancia de las estaciones piratas comerciales en el contexto europeo fue tan grande que sus emisiones hicieron cambiar toda la programación de la radiodifusión de nuestro continente, pasando a una programación basada en la música ligera. Analizaremos el origen de este fenómeno para obtener una tipología y las repercusiones que tuvo este fenómeno en los modelos radiofónicos contemporáneos.The relevance of commercial pirate radio stations in Europe has been so far-reaching that its broadcasts have totally transformed all radio programming on this continent. The present article analyses the origin of this phenomenon in order to obtain a typology and see the repercussions this phenomenon has had on contemporary radio models

Innovación en educación física: el kickboxing como contenido educativo

La innovación es un proceso necesario para avanzar en un sistema educativo que se apoya en los contenidos curriculares como una de las formas de representación más destacadas de toda realidad pedagógica. Esta demandada innovación puede ser solventada gracias a la inclusión de contenidos novedosos. El kickboxing pertenece a los deportes de combate que, tradicionalmente, no han sido integrados en las clases de educación física por miedo, desconocimiento o falsos estereotipos. Este artículo presenta una experiencia de investigación­acción sobre la introducción del kickboxing en las aulas de educación primaria a través del juego simple y sociali­zador, sin contacto entre los estudiantes y apoyado en las competencias motrices y morales que este deporte desarrolla. El objetivo era el desarrollo no solo físico, sino también social y ético. La respuesta recibida del alumnado fue muy satisfactoria