A density functional theory study of hydrogen dissociation and diffusion at the perimeter sites of Au/TiO2

Reactivity of supported gold catalysts is a hot topic in catalysis for many years. This communication reports an investigation on the dissociation of molecular hydrogen at the perimeter sites of Au/TiO2 and the spillover of hydrogen atoms from the gold to the support using density functional theory calculations. It is found that the heterolytic dissociation is favoured in comparison with homolytic dissociation of molecular hydrogen at the perimeter sites. However, the surface oxygen of the rutile TiO2(110) surface at these sites can be readily passivated by the formed OH, suggesting that further dissociation of molecular hydrogen may occur at pure gold sites.

Acrolein hydrogenation on Pt(211) and Au(211) surfaces:a density functional theory study

Partial hydrogenation of acrolein, the simplest alpha, beta-unsaturated aldehyde, is not only a model system to understand the selectivity in heterogeneous catalysis, but also technologically an important reaction. In this work, the reaction on Pt(211) and Au(211) surfaces is thoroughly investigated using density functional theory calculations. The formation routes of three partial hydrogenation products, namely propenol, propanal and enol, on both metals are studied. It is found that the pathway to produce enol is kinetically favoured on Pt while on Au the route of forming propenol is preferred. Our calculations also show that the propanal formation follows an indirect pathway on Pt(211). An energy decomposition method to analyze the barrier is utilized to understand the selectivities at Pt(211) and Au(211), which reveals that the interaction energies between the reactants involved in the transition states play a key role in determining the selectivity difference.

Examining the redox and formate mechanisms for water-gas shift reaction on Au/CeO2 using density functional theory

We perform DFT calculations to investigate the redox and formate mechanisms of water-gas-shift (WGS) reaction on Au/CeO2 catalysts. In the redox mechanism, we analyze all the key elementary steps and find that the OH cleavage is the key step. Three possible pathways of OH cleavage are calculated: (1) OHad '' + *'--> H-ad' + O-ad"; (2) H-ad' + OHad '' --> H-2(g) + O-ad '' + *'; and (3) OHad" + OHad '' --> 2O(ad '') + H-2(g) (*': the free adsorption sites on the oxides; ad': adsorption on the metal; ad": adsorption on the oxide, respectively). In the formate mechanism, we identify all the possible pathways for the formation and decomposition of surface formates in the WGS reaction. It is found that there is a shortcoming in the redox and formate mechanisms which is related to surface oxygen reproduction. Four possible pathways for producing surface oxygen are studied, and all the barriers of the four pathways are more than 1 eV. Our results suggest that the processes to reproduce surface oxygen in the reaction circle are not kinetically easy. (C) 2008 Elsevier B.V. All rights reserved.

Renouveau religieux et politique au Mozambique: entre permanence, rupture et historicité

La recherche sur le religieux en Afrique s’est beaucoup intéressée, ces vingt dernières années, au phénomène du « renouveau religieux », et elle s’est plutôt penchée sur la question des ruptures et des innovations qui en résultent. Le présent article interroge la réalité ce renouveau et explore, sur la base d’une étude de cas, la question des continuités et des ruptures dans les changements survenus  [1]. Tout d’abord, il s’intéresse à la nature du renouveau religieux au Mozambique ; il examine ensuite les continuités historiques et dénominationnelles existantes au sein du renouveau pour discuter, dans une troisième section, l’impact des transformations religieuses sur la relation entre religion et politique. La conclusion tente, elle, de faire la part entre ruptures et permanences, et d’appréhender la question du renouveau au-delà de cette dichotomie.

Penser la guerre au XXIe siècle

Ce numéro était déjà sous presse quand, le 13 novembre 2015, Paris était une nouvelle fois la cible d’attentats terroristes d’une ampleur sans précédent, faisant plus d’une centaine de morts. Le Président François Hollande parla cette fois, de manière répétée, d’‘un acte de guerre’. Des voix solidaires se sont élevées des quatre coins de la planète, soulignant bien que, à travers la France, ce sont bien les valeurs qu’elle représente et qu’elle partage avec nombre de pays que les assassins de Daech visaient. Parmi tous les messages de solidarité, il nous semble important de souligner celui d’Hassan Rohani, le Président iranien, et celui d’Abdelaziz Bouteflika, le Président algérien: immédiatement, le premier ‘condamn[ait] avec vigueur ces crimes contre l'humanité et présent[ait] [s]es condoléance au peuple français endeuillé et au gouvernement’; le second dénonçait sans réserve ‘cette horreur planifiée [qui] constitue un véritable crime contre l'humanité’. Quant à Anouar Kbibech, le nouveau président du Conseil français du culte musulman, il ‘condamn[ait] avec la plus grande vigueur ces attaques inqualifiables’ et ‘appel[ait] à se regrouper autour de ces valeurs qui font la France’. Plus que jamais, il faut éviter les amalgames pour ne pas faire le jeu des minorités extrémistes.

A facile method for the synthesis of Au/PEDOT:PSS nanocomposite

In this work, we have successfully synthesized Au nanoparticles (NPs) in situ in PEDOT:PSS deploying a room temperature atmospheric pressure microplasma. The size of the AuNPs is a function of the gold salt precursor concentration and the plasma processing time. The Au/polymer colloids after processing remain well dispersed over a prolonged period of time. Both gold salt concentration and the plasma processing time have influence on the electrical conductivity of the dried Au/PEDOT:PSS nanocomposite films. An enhanced electrical conductivity of the Au/PEDOT:PSS nanocomposite films has been attributed to (i) the interfacial ligand formation between the S atoms in PEDOT:PSS molecules and the Au surface and (ii) charge transfer from the AuNPs to the holes of PEDOT:PSS molecules.

A facile method for synthesizing PVA/Au, PVA/Ag and PVA/AuAg nanocomposites

In this paper, we presented a facile way of preparing PVA/Au, PVA/Ag and PVA/AuAg nanocomposites through in situ synthesis of metal nanoparticles in PVA hydrogel network using a room temperature atmospheric pressure microplasma. This is the first time microplasma technology is used for the fabrication of hydrogel based nanocomposites. The materials synthesized have been characterized for their microstructure and antibacterial properties. The nanoparticles synthesized within the PVA hydrogel network are found to be better dispersed than those synthesized in water, and their size and shape are more uniform. The new approach has opened a new avenue towards multi-scale synthesis of green and multi-functional nanocomposites, which may find wide range of potential applications in biomedical field.

Review of Michel Cahen, Les bandits. Un historien au Mozambique.

Book review of Michel Cahen, Les bandits. Un historien au Mozambique, 1994, Paris : Centre Culturel Calouste Gulbenkian, 2002, 351p., cartes, ISBN : 972-8462-28-X

The dust environment of comet 67P/Churyumov-Gerasimenko from Rosetta OSIRIS and VLT observations in the 4.5 to 2.9 au heliocentric distance range inbound

Context. The ESA Rosetta spacecraft, currently orbiting around comet 67P/Churyumov-Gerasimenko, has already provided in situ measurements of the dust grain properties from several instruments,particularly OSIRIS and GIADA. We propose adding value to those measurements by combining them with ground-based observations of the dust tail to monitor the overall, time-dependent dust-production rate and size distribution.
Aims. To constrain the dust grain properties, we take Rosetta OSIRIS and GIADA results into account, and combine OSIRIS data during the approach phase (from late April to early June 2014) with a large data set of ground-based images that were acquired with the ESO Very Large Telescope (VLT) from February to November 2014.
Methods. A Monte Carlo dust tail code, which has already been used to characterise the dust environments of several comets and active asteroids, has been applied to retrieve the dust parameters. Key properties of the grains (density, velocity, and size distribution) were obtained from Rosetta observations: these parameters were used as input of the code to considerably reduce the number of free parameters. In this way, the overall dust mass-loss rate and its dependence on the heliocentric distance could be obtained accurately.
Results. The dust parameters derived from the inner coma measurements by OSIRIS and GIADA and from distant imaging using VLT data are consistent, except for the power index of the size-distribution function, which is α = −3, instead of α = −2, for grains smaller than 1 mm. This is possibly linked to the presence of fluffy aggregates in the coma. The onset of cometary activity occurs at approximately 4.3 AU, with a dust production rate of 0.5 kg/s, increasing up to 15 kg/s at 2.9 AU. This implies a dust-to-gas mass ratio varying between 3.8 and 6.5 for the best-fit model when combined with water-production rates from the MIRO experiment.