634 research outputs found

    Comparing the Reaction Rates of Plasmonic (Gold) and Non-Plasmonic (Palladium) Metal Particles in Photocatalytic Hydrogen Production

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    Both Pd and Au metal particles are used in photocatalytic hydrogen generation. Yet while both act as electron sink only gold is poised to respond to visible light due to its plasmonic response. In order to quantitatively gauge their relative contribution into the reaction, the photocatalytic H2 production, from Au/TiO2 and Pd/TiO2 catalysts was studied under UV and UV–Vis light. While under UV light excitation, a weak dependence on the work function of the metal is observed, under UV–Vis light, Au is found to be twice more active than Pd. Under identical UV–Vis light irradiation, the turn over frequency calculated from XPS at.% is found to be 2.8 and 1.8 s−1 for Au and Pd, respectively. The effect is far more pronounced when the rates are normalized to the number of particles of each metal. Both the semiconductor TiO2 (UV light) and the plasmonic metal (visible light) need to be excited for the enhancement to occur; visible light alone causes a negligible reaction rate. Photocurrent measurements further confirmed the difference in the photocatalytic activity under UV and UV–Vis light excitation. Moreover, because of the presence of Au particles responding to visible light the reaction rate is enhanced due to “light penetration depth” effect

    Size and Shape Dependence of the Electronic Structure of Gold Nanoclusters on TiO2

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    Understanding the mechanism behind the superior catalytic power of single- or few-atom heterogeneous catalysts has become an important topic in surface chemistry. This is particularly the case for gold, with TiO2 being an efficient support. Here we use scanning tunneling microscopy/spectroscopy with theoretical calculations to investigate the adsorption geometry and local electronic structure of several-atom Au clusters on rutile TiO2(110), with the clusters fabricated by controlled manipulation of single atoms. Our study confirms that Au1 and Au2 clusters prefer adsorption at surface O vacancies. Au3 clusters adsorb at O vacancies in a linear-chain configuration parallel to the surface; in the absence of O vacancies they adsorb at Ti5c sites with a structure of a vertically pointing upright triangle. We find that both the electronic structure and cluster–substrate charge transfer depend critically on the cluster size, bonding configuration, and local environment. This suggests the possibility of engineering cluster selectivity for specific catalytic reactions

    Metal-Support Interactions and C1 Chemistry: Transforming Pt-CeO2into a Highly Active and Stable Catalyst for the Conversion of Carbon Dioxide and Methane

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    There is an ongoing search for materials which can accomplish the activation of two dangerous greenhouse gases like carbon dioxide and methane. In the area of C1 chemistry, the reaction between CO2 and CH4 to produce syngas (CO/H2), known as methane dry reforming (MDR), is attracting a lot of interest due to its green nature. On Pt(111), high temperatures must be used to activate the reactants, leading to a substantial deposition of carbon which makes this metal surface useless for the MDR process. In this study, we show that strong metal-support interactions present in Pt/CeO2(111) and Pt/CeO2 powders lead to systems which can bind CO2 and CH4 well at room temperature and are excellent and stable catalysts for the MDR process at moderate temperature (500 °C). The behavior of these systems was studied using a combination of in situ/operando methods (AP-XPS, XRD, and XAFS) which pointed to an active Pt-CeO2-x interface. In this interface, the oxide is far from being a passive spectator. It modifies the chemical properties of Pt, facilitating improved methane dissociation, and is directly involved in the adsorption and dissociation of CO2 making the MDR catalytic cycle possible. A comparison of the benefits gained by the use of an effective metal-oxide interface and those obtained by plain bimetallic bonding indicates that the former is much more important when optimizing the C1 chemistry associated with CO2 and CH4 conversion. The presence of elements with a different chemical nature at the metal-oxide interface opens the possibility for truly cooperative interactions in the activation of C-O and C-H bonds.Fil: Zhang, Feng. State University of New York. Stony Brook University; Estados UnidosFil: Gutiérrez, Ramón A.. Universidad Central de Venezuela; VenezuelaFil: Lustemberg, Pablo German. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Física de Rosario. Universidad Nacional de Rosario. Instituto de Física de Rosario; Argentina. Consejo Superior de Investigaciones Científicas; EspañaFil: Liu, Zongyuan. Brookhaven National Laboratory; Estados UnidosFil: Rui, Ning. Brookhaven National Laboratory; Estados UnidosFil: Wu, Tianpin. Argonne National Laboratory; Estados UnidosFil: Ramírez, Pedro J.. Zoneca-cenex; México. Universidad Central de Venezuela; VenezuelaFil: Xu, Wenqian. Argonne National Laboratory; Estados UnidosFil: Idriss, Hicham. King Abdullah University of Science and Technology; Arabia SauditaFil: Ganduglia Pirovano, M. Verónica. Consejo Superior de Investigaciones Científicas; EspañaFil: Senanayake, Sanjaya D.. Brookhaven National Laboratory; Estados UnidosFil: Rodriguez, José A.. Brookhaven National Laboratory; Estados Unidos. State University of New York. Stony Brook University; Estados Unido

    COVID‐19, nationalism, and the politics of crisis: A scholarly exchange

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    In this article, several scholars of nationalism discuss the potential for the COVID‐19 pandemic to impact the development of nationalism and world politics. To structure the discussion, the contributors respond to three questions: (1) how should we understand the relationship between nationalism and COVID‐19; (2) will COVID‐19 fuel ethnic and nationalist conflict; and (3) will COVID‐19 reinforce or erode the nation‐state in the long run? The contributors formulated their responses to these questions near to the outset of the pandemic, amid intense uncertainty. This made it acutely difficult, if not impossible, to make predictions. Nevertheless, it was felt that a historically and theoretically informed discussion would shed light on the types of political processes that could be triggered by the COVID‐19 pandemic. In doing so, the aim is to help orient researchers and policy‐makers as they grapple with what has rapidly become the most urgent issue of our times

    Engineering characterization of ground motion. Task I. Effects of characteristics of free-field motion on structural response

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    This report presents the results of the first task of a two-task study on the engineering characterization of earthquake ground motion for nuclear power plant design. The overall objective of this study is to develop recommendations for methods for selecting design response spectra or acceleration time histories to be used to characterize motion at the foundation level of nuclear power plants. Task I of the study develops a basis for selecting design response spectra, taking into account the characteristics of free-field ground motion found to be significant in causing structural damage
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