Pt-CeO2 catalysts synthesized by glucose assisted hydrothermal method: impact of calcination parameters on the structural properties and catalytic performance in PROX-CO

FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL E NÍVEL SUPERIORWe synthesized Pt supported catalysts by the glucose assisted hydrothermal method, in which a carbon template was used to form a porous CeO2 structure upon calcination. Special emphasis was given to evaluate the influence of calcination parameters in the18534053412FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL E NÍVEL SUPERIORFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL E NÍVEL SUPERIOR2011/50727-9t 2014/21988-7306242/2010-4309373/2014-0sem informaçã

Communication: theoretical exploration of Au+H2, D2, and HD reactive collisions

The following article appeared in Journal of Chemical Physic 135.9 (2011): 091102 and may be found at http://scitation.aip.org/content/aip/journal/jcp/135/9/10.1063/1.3635772A quasi-classical study of the endoergic Au(1S)+ H2(X1Σg+) → AuHAuH+(2Σ+)+H(2S) reaction, and isotopic variants, is performed to compare with recent experimental results [F. Li, C. S. Hinton, M. Citir, F. Liu, and P. B. Armentrout, J. Chem. Phys. 134, 024310 (2011)]. For this purpose, a new global potential energy surface has been developed based on multi-reference configuration interaction ab initio calculations. The quasi-classical trajectory results show a very good agreement with the experiments, showing the same trends for the different isotopic variants of the hydrogen molecule. It is also found that the total dissociation into three fragments, Au+H+H, is the dominant reaction channel for energies above the H2 dissociation energy. This results from a well in the entrance channel of the potential energy surface, which enhances the probability of H-Au-H insertionA.D.-U. acknowledges a JAE fellowship supported by CSIC. This work is supported by Comunidad Autónoma de Madrid, Grant No. S2009/MAT/1467, and by Ministerio de Ciencia e Innovación, Grant Nos. CSD2009-00038 and FIS2010-18132. The calculations have been performed at CESGA and IFF computing centers. P.B.A. thanks the National Science Foundation for suppor

Chirality in Bare and Passivated Gold Nanoclusters

Chiral structures have been found as the lowest-energy isomers of bare (Au$_{28}$ and Au$_{55}) and thiol-passivated (Au$_{28}(SCH$_{3})$_{16}$and Au$_{38}(SCH_{3})_{24}) gold nanoclusters. The degree of chirality existing in the chiral clusters was calculated using the Hausdorff chirality measure. We found that the index of chirality is higher in the passivated clusters and decreases with the cluster size. These results are consistent with the observed chiroptical activity recently reported for glutahione-passivated gold nanoclusters, and provide theoretical support for the existence of chirality in these novel compounds.Comment: 5 pages, 1 figure. Submitted to PR

Towards a Tetravalent Chemistry of Colloids

We propose coating spherical particles or droplets with anisotropic nano-sized objects to allow micron-scale colloids to link or functionalize with a four-fold valence, similar to the sp3 hybridized chemical bonds associated with, e.g., carbon, silicon and germanium. Candidates for such coatings include triblock copolymers, gemini lipids, metallic or semiconducting nanorods and conventional liquid crystal compounds. We estimate the size of the relevant nematic Frank constants, discuss how to obtain other valences and analyze the thermal distortions of ground state configurations of defects on the sphere.Comment: Replaced to improve figures. 4 figures Nano Letter

Molecular dynamics simulations of lead clusters

Molecular dynamics simulations of nanometer-sized lead clusters have been performed using the Lim, Ong and Ercolessi glue potential (Surf. Sci. {\bf 269/270}, 1109 (1992)). The binding energies of clusters forming crystalline (fcc), decahedron and icosahedron structures are compared, showing that fcc cuboctahedra are the most energetically favoured of these polyhedral model structures. However, simulations of the freezing of liquid droplets produced a characteristic form of ``shaved'' icosahedron, in which atoms are absent at the edges and apexes of the polyhedron. This arrangement is energetically favoured for 600-4000 atom clusters. Larger clusters favour crystalline structures. Indeed, simulated freezing of a 6525-atom liquid droplet produced an imperfect fcc Wulff particle, containing a number of parallel stacking faults. The effects of temperature on the preferred structure of crystalline clusters below the melting point have been considered. The implications of these results for the interpretation of experimental data is discussed.Comment: 11 pages, 18 figues, new section added and one figure added, other minor changes for publicatio

Spatial distribution of far-infrared rotationally excited CH⁺ and OH emission lines in the Orion Bar photodissociation region

Context. The methylidyne cation (CH+) and hydroxyl (OH) are key molecules in the warm interstellar chemistry, but their formation and excitation mechanisms are not well understood. Their abundance and excitation are predicted to be enhanced by the presence of vibrationally excited H2 or hot gas (~500−1000 K) in photodissociation regions (PDRs) with high incident far-ultraviolet (FUV) radiation field. The excitation may also originate in dense gas (>105 cm-3) followed by nonreactive collisions with H2, H, and electrons. Previous observations of the Orion Bar suggest that the rotationally excited CH+ and OH correlate with the excited CO, which is a tracer of dense and warm gas, and that formation pumping contributes to CH+ excitation.Aims. Our goal is to examine the spatial distribution of the rotationally excited CH+ and OH emission lines in the Orion Bar to establish their physical origin and main formation and excitation mechanisms.Methods. We present spatially sampled maps of the CH+ J = 3–2 transition at 119.8 μm and the OH Λ doublet at 84 μm in the Orion Bar over an area of 110″× 110″ with Herschel/PACS. We compare the spatial distribution of these molecules with those of their chemical precursors, C+ , O and H2, and tracers of warm and dense gas (high- J CO). We assess the spatial variation of the CH+ J = 2–1 velocity-resolved line profile at 1669 GHz with Herschel/HIFI spectrometer observations.Results. The OH and especially CH+ lines correlate well with the high-J CO emission and delineate the warm and dense molecular region at the edge of the Bar. While notably similar, the differences in the CH+ and OH morphologies indicate that CH+ formation and excitation are strongly related to the observed vibrationally excited H2. This, together with the observed broad CH+ line widths, indicates that formation pumping contributes to the excitation of this reactive molecular ion. Interestingly, the peak of the rotationally excited OH 84 μm emission coincides with a bright young object, proplyd 244–440, which shows that OH can be an excellent tracer of UV-irradiated dense gas.Conclusions. The spatial distribution of CH+ and OH revealed in our maps is consistent with previous modeling studies. Both formation pumping and nonreactive collisions in a UV-irradiated dense gas are important CH+ J = 3–2 excitation processes. The excitation of the OH Λ doublet at 84 μm is mainly sensitive to the temperature and density

Molecular excitation in the Interstellar Medium: recent advances in collisional, radiative and chemical processes

We review the different excitation processes in the interstellar mediumComment: Accepted in Chem. Re