O2Activation over Ag-Decorated CeO2(111) and TiO2(110) Surfaces: A Theoretical Comparative Investigation

Periodic spin-polarized hybrid density functional theory calculations have been performed to investigate the reactivity of pristine, O-defective, and Ag-decorated CeO2(111) and TiO2(110) surfaces with a small Ag10 cluster toward O2. The adsorption of O2 and its subsequent dissociation have been studied in order to provide a better understanding of the role of the oxide, the metallic nanoparticle, and their interaction in the reactivity of composite metal/metal oxide materials toward O2, as potential catalysts to this reaction. Structural, energetic, electronic, and vibrational properties of all species involved in the different reaction paths considered have been fully characterized. On the stoichiometric surfaces, Ag10 is oxidized and reduces surface Ce4+/Ti4+ ions, while on the O-defective surfaces, the adhesion of silver is promoted only on CeO2 but unfavored on TiO2. On the other hand, on the silver-free supports, O2 strongly adsorbs at vacancies and preferentially reduces to peroxide. When no O vacancies are considered on the Ag10-decorated supports, the net positive charge on Ag10 actually prevents the adsorption and reduction of O2. Instead, when O vacancies are included, two reaction pathways are observed; oxygen molecules can weakly absorb on the silver cluster as a superoxide moiety or strongly adsorb at the vacancy as peroxide. The dissociation of the O-O bond of the peroxide is favored both from the thermodynamic and kinetic points of view in silver-decorated surfaces, in contrast with the silver-free cases. In addition, Ag10/CeO2 shows higher activity toward the O2 adsorption and dissociation than Ag10/TiO2, which can be related both to the higher ionicity and superior electron storage/release ability of ceria with respect to titania, thus leading to the weakening of the O-O bond and providing lower activation barriers for oxygen reduction. These results deepen the current understanding of the reactivity of metal/metal oxide composites toward O2, especially elucidating how the surface stoichiometry affects the charge state of the metal clusters, and hence the reactivity of these interfaces toward O2, with potential important consequences when such composites are considered for catalytic applications

Іван Франко - публіцист

Проаналізовано соціально-економічну і культурно-освітню публіцистику І. Франка, зокрема, його ставлення до податкової політики Австро-Угорщини, діяльності банківської системи, еміграції з Галичини, кооперативного руху, майбутнього української держави.The article analyses social and economic and cultural and educational publications by Ivan Franko, as well as his attitude to tax policies in Austro-Hungarian Empire, banking system activities, emigration from Halychyna, co-operative societies movement, and the future of Ukraine

Fast Measurements of the Electron Beam Transverse Size and Position on SOLEIL Storage Ring

On SOLEIL storage ring, three beamlines are dedicated to electron beam diagnostics: two in the X-ray range and one in the visible range. The visible range beamline uses the synchrotron radiation which is emitted in one of the ring dipoles and further extracted by a slotted mirror operated in surf-mode (surfing on the upper part of the synchrotron layer). The radiation in the visible range is then transported towards a diagnostic hutch in the experimental hall, allowing electron beam imaging at the source point onto a standard CCD camera. In the perspective of prototyping works for the eventually forthcoming upgrade of SOLEIL, and for the on-going commissioning of a new Multipole Injection Kicker (MIK), we recently installed in this hutch two new branches ended by two new cameras (a KALYPSO system and a standard CMOS camera). We report in this paper the optimization we performed on the mirror mode of operation, as well as on spectral filtering, polarization selection, image plane location, fast acquisition tools, to improve the resolution and increase the speed of our initial transverse beam size measurement at source point

The ARC-EN-CIEL radiation sources

MOPC005International audienceThe ARC-EN-CIEL (Accelerator-Radiation for Enhanced Coherent Intense Extended Light) project proposes a panoply of light sources for the scientific community on a 1 GeV superconducting LINAC (phase 2) on which two ERL loops (1 and 2 GeV) are added in phase 3. LEL1 (200-1.5 nm), LEL2 (10-0.5 nm) and LEL4 (2-0.2 nm) are three kHz High Gain Harmonic Generation Free Electron Laser sources seeded with the High order Harmonics generated in Gas, with 100-30 FWHM pulses. A collaboration, which has been set-up with the SCSS Prototype Accelerator in Japan to test this key concept of ARC-EN-CIEL, has led to the experimental demonstration of the seeding with HHG and the observation up the 7th non linear harmonic with a seed at 160 nm. LEL3 (40-8 nm) installed on the 1 GeV loop is a MHz FEL oscillator providing higher average power and brilliance. In addition, in vacuum undulator spontaneous emission source extend the spectral range above 10 keV and intense THz radiation is generated by edge radiation of bending magnets. Optimisations and light sources characteristics are described

Conservation et introduction de lémuriens sur l'îlot Mbouzy (Mayotte)

À Mayotte, l'îlot Mbouzi est un lieu remarquable par son milieu naturel en grande partie préservé, alors qu'il se situe à proximité de la ville principale, Mamoudzou. Il fait l'objet d'une demande de classement en réserve naturelle. Nous pensons utile d'apporter quelques éléments pouvant servir à la réflexion sur l'avenir de cet îlot, et d'établir une sorte d'état des lieux concernant son intérêt biologique. Quelles sont les possibilités d'équilibre à long terme entre les populations animales et végétales, sachant qu'une association (loi de 1901) consacr

Combined coherent x-ray micro-diffraction and local mechanical loading on copper nanocrystals

Coherent x-ray micro-diffraction and local mechanical loading can be combined to investigate the mechanical deformation in crystalline nanostructures. Here we present measurements of plastic deformation in a copper crystal of sub-micron size obtained by loading the sample with an Atomic Force Microscopy tip. The appearance of sharp features in the diffraction pattern, while conserving its global shape, is attributed to crystal defects induced by the tip

The future of mammary stem cell biology: the power of in vivo transplants

The recent review by Smith and Medina [1] of in vivo transplantation models and their role in investigating mammary stem cell (MaSC) biology provides comprehensive coverage of the history and complexity of the ‘gold standard ’ MaSC assay in mice. This includes a description of the pioneering studies that showed that mammary epithelial outgrowths can be generated in cleared mammary fat pads transplanted with explants or admixtures of mammary cells [2]. However, this approach clearly does not lend itself to prospective analysis of isolated subpopulations in order to identify which cells possess in vivo regenerative activity. More recently, success in obtaining complex mammary gland structures from transplanted suspensions of single cells has now made this possible [3-7]. Moreover, the regenerated structures have been shown to contain daughter cells with the same in viv

Multi-time-scale hydroclimate dynamics of a regional watershed and links to large-scale atmospheric circulation:Application to the Seine river catchment, France

(IF 3.73; Q1)International audienceIn the present context of global changes, considerable efforts have been deployed by the hydrological scientific community to improve our understanding of the impacts of climate fluctuations on water resources. Both observational and modeling studies have been extensively employed to characterize hydrological changes and trends, assess the impact of climate variability or provide future scenarios of water resources. In the aim of a better understanding of hydrological changes, it is of crucial importance to determine how and to what extent trends and long-term oscillations detectable in hydrological variables are linked to global climate oscillations.In this work, we develop an approach associating correlation between large and local scales, empirical statistical downscaling and wavelet multiresolution decomposition of monthly precipitation and streamflow over the Seine river watershed, and the North Atlantic sea level pressure (SLP) in order to gain additional insights on the atmospheric patterns associated with the regional hydrology. We hypothesized that: (i) atmospheric patterns may change according to the different temporal wavelengths defining the variability of the signals; and (ii) definition of those hydrological/circulation relationships for each temporal wavelength may improve the determination of large-scale predictors of local variations.The results showed that the links between large and local scales were not necessarily constant according to time-scale (i.e. for the different frequencies characterizing the signals), resulting in changing spatial patterns across scales. This was then taken into account by developing an empirical statistical downscaling (ESD) modeling approach, which integrated discrete wavelet multiresolution analysis for reconstructing monthly regional hydrometeorological processes (predictand: precipitation and streamflow on the Seine river catchment) based on a large-scale predictor (SLP over the Euro-Atlantic sector). This approach basically consisted in three steps: 1 – decomposing large-scale climate and hydrological signals (SLP field, precipitation or streamflow) using discrete wavelet multiresolution analysis, 2 – generating a statistical downscaling model per time-scale, 3 – summing up all scale-dependent models in order to obtain a final reconstruction of the predictand. The results obtained revealed a significant improvement of the reconstructions for both precipitation and streamflow when using the multiresolution ESD model instead of basic ESD. In particular, the multiresolution ESD model handled very well the significant changes in variance through time observed in either precipitation or streamflow. For instance, the post-1980 period, which had been characterized by particularly high amplitudes in interannual-to-interdecadal variability associated with alternating flood and extremely low-flow/drought periods (e.g., winter/spring 2001, summer 2003), could not be reconstructed without integrating wavelet multiresolution analysis into the model. In accordance with previous studies, the wavelet components detected in SLP, precipitation and streamflow on interannual to interdecadal time-scales could be interpreted in terms of influence of the Gulf-Stream oceanic front on atmospheric circulation