Structure sensitivity of selective acetylene hydrogenation over the catalysts with shape-controlled palladium nanoparticles

The structure sensitivity of acetylene hydrogenation on catalysts with controlled shape of palladium nanoparticles was studied. Palladium particles of cubic (Pdcub), cuboctahedral (Pdco) and octahedral (Pdoct) shapes were obtained by a colloidal method. Poly(N-vinyl)pyrrolidone (PVP) was used as the stabilizer of colloidal solutions. In order to eliminate the effect of the polymer on the properties of the catalyst, PVP was removed from the surface of the particles after their transfer to the support by simultaneous treatment with ozone and UV radiation. This allowed complete cleaning of the catalyst surface from the organic stabilizer without any change in the morphology of particles. The effectiveness of this treatment method was confirmed by X-ray photoelectron spectroscopy and scanning electron microscopy. It was found experimentally that the shape of nanoparticles does not influence the catalyst selectivity, but the activity decreases in the order Pdoct > Pdco > Pdcub. Since octahedrons consist of (111) faces, the cubes contain only (100) faces, and the cuboctahedrons are composed of faces of both types, Pd111 is more active than Pd100. Calculations with the use of a statistical method showed that the ∼3-nm Pd octahedrons are nanoparticles with optimum shape and size, giving maximum catalyst activit

Structure sensitivity of selective acetylene hydrogenation over the catalysts with shape-controlled palladium nanoparticles

The structure sensitivity of acetylene hydrogenation on catalysts with controlled shape of palladium nanoparticles was studied. Palladium particles of cubic (Pd-cub), cuboctahedral (Pd-co) and octahedral (Pd-oct) shapes were obtained by a colloidal method. Poly(N-vinyl)pyrrolidone (PVP) was used as the stabilizer of colloidal solutions. In order to eliminate the effect of the polymer on the properties of the catalyst, PVP was removed from the surface of the particles after their transfer to the support by simultaneous treatment with ozone and UV radiation. This allowed complete cleaning of the catalyst surface from the organic stabilizer without any change in the morphology of particles. The effectiveness of this treatment method was confirmed by X-ray photoelectron spectroscopy and scanning electron microscopy. It was found experimentally that the shape of nanoparticles does not influence the catalyst selectivity, but the activity decreases in the order Pd-oct > Pd-co > Pd-cub. Since octahedrons consist of (111) faces, the cubes contain only (100) faces, and the cuboctahedrons are composed of faces of both types, Pd-111 is more active than Pd-100. Calculations with the use of a statistical method showed that the similar to 3-nm Pd octahedrons are nanoparticles with optimum shape and size, giving maximum catalyst activity

The Aguablanca Ni–(Cu) sulfide deposit, SW Spain: geologic and geochemical controls and the relationship with a midcrustal layered mafic complex

The Aguablanca Ni–(Cu) sulfide deposit is hosted by a breccia pipe within a gabbro–diorite pluton. The deposit probably formed due to the disruption of a partially crystallized layered mafic complex at about 12– 19 km depth and the subsequent emplacement of melts and breccias at shallow levels (<2 km). The ore-hosting breccias are interpreted as fragments of an ultramafic cumulate, which were transported to the near surface along with a molten sulfide melt. Phlogopite Ar–Ar ages are 341– 332 Ma in the breccia pipe, and 338–334 Ma in the layered mafic complex, and are similar to recently reported U–Pb ages of the host Aguablanca Stock and other nearby calcalkaline metaluminous intrusions (ca. 350–330 Ma). Ore deposition resulted from the combination of two critical factors, the emplacement of a layered mafic complex deep in the continental crust and the development of small dilational structures along transcrustal strike-slip faults that triggered the forceful intrusion of magmas to shallow levels. The emplacement of basaltic magmas in the lower middle crust was accompanied by major interaction with the host rocks, immiscibility of a sulfide melt, and the formation of a magma chamber with ultramafic cumulates and sulfide melt at the bottom and a vertically zoned mafic to intermediate magmas above. Dismembered bodies of mafic/ultramafic rocks thought to be parts of the complex crop out about 50 km southwest of the deposit in a tectonically uplifted block (Cortegana Igneous Complex, Aracena Massif). Reactivation of Variscan structures that merged at the depth of the mafic complex led to sequential extraction of melts, cumulates, and sulfide magma. Lithogeochemistry and Sr and Nd isotope data of the Aguablanca Stock reflect the mixing from two distinct reservoirs, i.e., an evolved siliciclastic middle-upper continental crust and a primitive tholeiitic melt. Crustal contamination in the deep magma chamber was so intense that orthopyroxene replaced olivine as the main mineral phase controlling the early fractional crystallization of the melt. Geochemical evidence includes enrichment in SiO2 and incompatible elements, and Sr and Nd isotope compositions (87Sr/86Sri 0.708–0.710; 143Nd/144Ndi 0.512–0.513). However, rocks of the Cortegana Igneous Complex have low initial 87Sr/86Sr and high initial 143Nd/144Nd values suggesting contamination by lower crustal rocks. Comparison of the geochemical and geological features of igneous rocks in the Aguablanca deposit and the Cortegana Igneous Complex indicates that, although probably part of the same magmatic system, they are rather different and the rocks of the Cortegana Igneous Complex were not the direct source of the Aguablanca deposit. Crust–magma interaction was a complex process, and the generation of orebodies was controlled by local but highly variable factors. The model for the formation of the Aguablanca deposit presented in this study implies that dense sulfide melts can effectively travel long distances through the continental crust and that dilational zones within compressional belts can effectively focus such melt transport into shallow environments

Relationship between olive oil consumption and ankle-brachial pressure index in a population at high cardiovascular risk

The aim of this study was to ascertain the association between the consumption of different categories of edible olive oils (virgin olive oils and olive oil) and olive pomace oil and ankle-brachial pressure index (ABI) in participants in the PREDIMED-Plus study, a trial of lifestyle modification for weight and cardiovascular event reduction in individuals with overweight/obesity harboring the metabolic syndrome. Methods: We performed a cross-sectional analysis of the PREDIMED-Plus trial. Consumption of any category of olive oil and olive pomace oil was assessed through a validated food-frequency questionnaire. Multivariable linear regression models were fitted to assess associations between olive oil consumption and ABI. Additionally, ABI ≤1 was considered as the outcome in logistic models with different categories of olive oil and olive pomace oil as exposure. Results: Among 4330 participants, the highest quintile of total olive oil consumption (sum of all categories of olive oil and olive pomace oil) was associated with higher mean values of ABI (beta coefficient: 0.014, 95% confidence interval [CI]: 0.002, 0.027) (p for trend = 0.010). Logistic models comparing the consumption of different categories of olive oils, olive pomace oil and ABI ≤1 values revealed an inverse association between virgin olive oils consumption and the likelihood of a low ABI (odds ratio [OR] 0.73, 95% CI [0.56, 0.97]), while consumption of olive pomace oil was positively associated with a low ABI (OR 1.22 95% CI [1.00, 1.48]). Conclusions: In a Mediterranean population at high cardiovascular risk, total olive oil consumption was associated with a higher mean ABI. These results suggest that olive oil consumption may be beneficial for peripheral artery disease prevention, but longitudinal studies are needed

Humanizar emprendiendo: homenaje a Rafael Alvira

Este cuaderno contiene "El Instituto y Rafael Alvira" "La carta 9 de Séneca" "Rafael Alvira: la castiza filosofía del hombre que vuelve" "Añoranza del humanismo necesario" "Una reflexión filosófica sobre lo económico: comentario a un texto de Rafael Alvira" "La dimensión societaria de la economía y de la empresa" "Sobre el espíritu aristocrático y el empresario: responsabilidades de ayer, responsabilidades de hoy" "Sobre el sistema de los derechos del hombre: el punto de vista de Charles Péguy" "El hogar familiar: espacio de lo eterno" "¿Filosofar con el martillo o con la empresa?" "Qué queremos decir cuando hablamos de desarrollo" "Tipologías de la información económico-financiera en la empresa. Valores y valoración" "Rafael Alvira y la Universidad de Montevideo" "Breve introducción al examen sistemático de “Cristianismo y empresarialidad”" "La realidad del poder en la familia y en la empresa familiar" "El todo y la parte. Alabanza de la sinécdoque" "Las raíces del liderazgo auténtico. Una fenomenología básica" "Algunas consideraciones sobre el poder político

A parameter-free total Lagrangian smooth particle hydrodynamics algorithm applied to problems with free surfaces

This paper presents a new Smooth Particle Hydrodynamics computational framework for the solution of inviscid free surface flow problems. The formulation is based on the Total Lagrangian description of a system of first-order conservation laws written in terms of the linear momentum and the Jacobian of the deformation. One of the aims of this paper is to explore the use of Total Lagrangian description in the case of large deformations but without topological changes. In this case, the evaluation of spatial integrals is carried out with respect to the initial undeformed configuration, yielding an extremely efficient formulation where the need for continuous particle neighbouring search is completely circumvented. To guarantee stability from the SPH discretisation point of view, consistently derived Riemann-based numerical dissipation is suitably introduced where global numerical entropy production is demonstrated via a novel technique in terms of the time rate of the Hamiltonian of the system. Since the kernel derivatives presented in this work are fixed in the reference configuration, the non-physical clumping mechanism is completely removed. To fulfil conservation of the global angular momentum, a posteriori (least-squares) projection procedure is introduced. Finally, a wide spectrum of dedicated prototype problems is thoroughly examined. Through these tests, the SPH methodology overcomes by construction a number of persistent numerical drawbacks (e.g. hour-glassing, pressure instability, global conservation and/or completeness issues) commonly found in SPH literature, without resorting to the use of any ad-hoc user-defined artificial stabilisation parameters. Crucially, the overall SPH algorithm yields equal second order of convergence for both velocities and pressure

Global patterns and drivers of ecosystem functioning in rivers and riparian zones

River ecosystems receive and process vast quantities of terrestrial organic carbon, the fate of which depends strongly on microbial activity. Variation in and controls of processing rates, however, are poorly characterized at the global scale. In response, we used a peer-sourced research network and a highly standardized carbon processing assay to conduct a global-scale field experiment in greater than 1000 river and riparian sites. We found that Earth's biomes have distinct carbon processing signatures. Slow processing is evident across latitudes, whereas rapid rates are restricted to lower latitudes. Both the mean rate and variability decline with latitude, suggesting temperature constraints toward the poles and greater roles for other environmental drivers (e.g., nutrient loading) toward the equator. These results and data set the stage for unprecedented "next-generation biomonitoring" by establishing baselines to help quantify environmental impacts to the functioning of ecosystems at a global scale.peerReviewe

Structure Sensitivity of 2\u2010Methyl--butyn-2-ol Hydrogenation on Pd: Computational and Experimental Modeling

In the frame of DFT paradigms, the adsorption of 2-methyl-3-butyn-2-ol (MBY) and 2-methyl-3-buten-2-ol (MBE) on a Pd-30 cluster, including both {100} and {111} faces, was studied along with the pathways involved in the hydrogenation, taking place on plane and low coordination (corner/edge) sites of given MBY/Pd-30 and MBE/Pd-30 surface configurations. The calculated energetics, further validated by gas-phase and water-assisted gas-phase MBY and MBE hydrogenation, performed on well-defined size and shape-controlled Pd nanoparticles supported on SiO2, were able to explain the origin of the structure sensitivity and the high selectivity characterizing the title reaction when occurring in aqueous solution. The C C moiety of the MBY surface species indeed seemed to be mostly activated by plane sites instead of corner/edge atoms, whereas the MBE species appeared to have a different behavior, with their C=C moieties typically being activated by low coordination sites. DFT studies excluded that the overhydrogenation paths could be affected by the site topologies; hence, the role of plane, edge, or corner atoms should not be influential in setting the surface reaction mechanism, which as a consequence could be controlled by the adsorption energy, actually distinguished by different values on sites of different topology. The role of water in the selectivity to MBE, which characterizes the catalytic overhydrogenation of MBY on I'd nanoparticles, was also inferred

Scalable Triple Cation Mixed Halide Perovskite–BiVO<inf>4</inf> Tandems for Bias-Free Water Splitting

Strong interest exists in the development of organic-inorganic lead halide perovskite photovoltaics and of photoelectrochemical (PEC) tandem absorber systems for solar fuel production. However, their scalability and durability have long been limiting factors. In this work, we reveal how both fields can be seamlessly merged together, to obtain scalable, bias-free solar water splitting tandem devices. For this purpose, state-of-the-art cesium formamidinium methylammonium (CsFAMA) triple cation mixed halide perovskite photovoltaic cells with a nickel oxide (NiOx) hole transport layer are employed to produce Field’s metal-epoxy encapsulated photocathodes. Their stability (up to 7h), photocurrent density (–12.1 0.3mAcm 2 at 0V vs.RHE) and reproducibility enables a matching combination with robust BiVO4 photoanodes, resulting in 0.25cm2 PEC tandems with an excellent stability of up to 20h and a bias-free solar-to-hydrogen efficiency of 0.35 0.14%. The high reliability of the fabrication procedures allows scaling of the devices up to 10cm2, with a slight decrease in bias-free photocurrent density from 0.39 0.15mAcm 2 to 0.23 0.10mAcm 2 due to an increasing series resistance. To characterise these devices, a versatile 3D-printed PEC cell was also developed. The modular PEC cell represents an affordable alternative to existing designs and can be easily adjusted for a broad range of samples. Overall, these findings shed further light on the factors required to bring both perovskite photovoltaics and photoelectrocatalysis into large-scale applications, revealing some key aspects for device fabrication, operation and implementation.Cambridge Trust, the Winton Programme of Physics of Sustainability, Magdalene College Cambridge, Marie cure Actions of the European Union's Seventh Framework Programme, Christian Doppler Research Association, OMV Group, ERC Starting Gran