Size-Dependent Dissociation of Carbon Monoxide on Cobalt Nanoparticles

[[abstract]]In situ soft X-ray absorption spectroscopy (XAS) was employed to study the adsorption and dissociation of carbon monoxide molecules on cobalt nanoparticles with sizes ranging from 4 to 15 nm. The majority of CO molecules adsorb molecularly on the surface of the nanoparticles, but some undergo dissociative adsorption, leading to oxide species on the surface of the nanoparticles. We found that the tendency of CO to undergo dissociation depends critically on the size of the Co nanoparticles. Indeed, CO molecules dissociate much more efficiently on the larger nanoparticles (15 nm) than on the smaller particles (4 nm). We further observed a strong increase in the dissociation rate of adsorbed CO upon exposure to hydrogen, clearly demonstrating that the CO dissociation on cobalt nanoparticles is assisted by hydrogen. Our results suggest that the ability of cobalt nanoparticles to dissociate hydrogen is the main parameter determining the reactivity of cobalt nanoparticles in Fischer–Tropsch synthesis.[[notice]]補正完畢[[incitationindex]]SCI[[booktype]]紙本[[booktype]]電子

Light-Promoted Hydrogenation of Carbon Dioxide¿An Overview

[EN] Hydrogenation of carbon dioxide is considered as a viable strategy to generate fuels while closing the carbon cycle (heavily disrupted by the abuse in the exploitation of fossil resources) and reducing greenhouse gas emissions. The process can be performed by heat-powered catalytic processes, albeit conversion and selectivity tend to be reduced at increasing temperatures owing to thermodynamic constraints. Recent investigations, as summarised in this overview, have proven that light activation is a distinct possibility for the promotion of CO2 hydrogenation to fuels. This effect is particularly beneficial in methanation processes, which can be enhanced under simulated solar irradiation using materials based on metallic nanoparticles as catalysts. The use of nickel, ruthenium and rhodium has led to substantial efficiencies. Light-promoted processes entail performances on a par with (or even superior to) those of thermally-induced, industrially-relevant, commercial technologies.The author thanks the Spanish Government (Ministerio de Economía y Competitividad, MINECO) for financial support via a project for young researchers (CTQ2015-74138-JIN), and the ‘‘Severo Ochoa’’ programme (SEV 2012-0267). The European Union is also acknowledged for the SynCatMatch project (ERCAdG-2014-671093)Puga Vaca, A. (2016). Light-Promoted Hydrogenation of Carbon Dioxide¿An Overview. Topics in Catalysis. 59(15-16):1268-1278. https://doi.org/10.1007/s11244-016-0658-zS126812785915-16Centi G, Perathoner S (2009) Opportunities and prospects in the chemical recycling of carbon dioxide to fuels. Catal Today 148:191–205Aresta M, Dibenedetto A, Angelini A (2014) Catalysis for the valorization of exhaust carbon: from CO2 to chemicals, materials, and fuels. technological use of CO2. 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Dealloying of Cobalt from CuCo Nanoparticles under Syngas Exposure

International audienceThe structure and composition of core−shell CuCo nanoparticles were found to change as a result of cleaning pretreatments and when exposed to syngas (CO + H 2) at atmospheric pressure. In situ X-ray absorption and photoelectron spectroscopies revealed the oxidation state of the particles as well as the presence of adsorbates under syngas. Transmission electron microscopy was used for ex situ analysis of the shape, elemental composition, and structure after reaction. The original core−shell structure was found to change to a hollow CuCo alloy after pretreatment by oxidation in pure O 2 and reduction in pure H 2. After 30 min of exposure to syngas, a significant fraction (5%) of the particles was strongly depleted in cobalt giving copper-rich nanoparticles. This fraction increased with duration of syngas exposure, a phenomenon that did not occur under pure CO or pure H 2. This study suggests that Co and Cu can each individually contribute to syngas conversion with CuCo catalysts

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Structural transitions at the nanoscale: the example of palladium phosphides synthesized from white phosphorus

International audienceStoichiometric reactions of Pd(0) nanoparticles with various amounts of white phosphorus (P-4) are an efficient route to convert them into the corresponding Pd phosphides PdxPy. Formation of crystallized palladium phosphide nanoparticles is a two-step process, which allows exploring in detail the phase transitions of the PdxPy system, from amorphous Pd-P nanoparticles (formed in a first step at moderate temperature) to crystallization (at higher temperature). The second temperature was found to be strongly dependent on the Pd/P ratio: PdP2, Pd5P2 and Pd3P stoichiometries form the amorphous phases, but only PdP2 and Pd5P2 could be further crystallized from them. Although it exists as a bulk crystalline material, Pd3P could only be crystallized by starting from the more Pd-rich Pd6P composition. Phase-to-phase transformations from P-poor phosphides (Pd3P and Pd5P2) to the P-rich PdP2 were also demonstrated, and a first Pd-P phase diagram at the nanoscale was tentatively produced

The Active State of Supported Ruthenium Oxide Nanoparticles during Carbon Dioxide Methanation

Ruthenium catalysts supported on TiO2 have been shown to have competitive activity and selectivity for the methanation of CO2. In particular, a catalyst using preformed RuO2 nanoparticles deposited on a TiO2 support showed competitive performances in a previous study. In this work, ambient-pressure X-ray photoelectron spectroscopy was employed to determine the chemical state of this catalyst under reaction conditions. The active state of ruthenium was found to be the metallic one. Surface adsorbates were monitored in the steady state, and CHx species were found to be favored over adsorbed carbon monoxide at increasing temperatures