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Ag surface segregation in nanoporous Au catalysts during CO oxidation.

ABSTRACT: The present study focuses on the modification of surface compositional profiles induced in nanoporous (NP) Au catalysts by the catalytic oxidation of carbon monoxide to carbon dioxide in the presence of oxygen. The phenomenon has deep implications concerning the catalytic behavior of NP Au foams in particular, and more in general for the design of more efficient catalysts. Aimed at gaining deeper insight into the mechanisms governing surface segregation, we exposed NP Au foams containing residual Ag to a mixture of gaseous carbon monoxide and oxygen at different temperature. Structural and surface composition analyses pointed out the concomitant occurrence of both NP Au coarsening and Ag surface segregation processes. Experimental findings suggest for Ag surface segregation a two-stage kinetics. During the initial, rapid coarsening of the NP Au structure, Ag surface segregation is mediated by surface rearrangements, which allow the Ag atoms to reach the surface at anomalously fast rate. As coarsening decelerates, the slower diffusion of buried Ag atoms towards the surface predominates, due to favorable chemical interactions with adsorbed oxygen. This novel mechanism's understanding can benefit strategic areas of science and technology.

SUBMITTER: Pia G

PROVIDER: S-EPMC6185915 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Catalytic activity of nanostructured Au: Scale effects versus bimetallic/bifunctional effects in low-temperature CO oxidation on nanoporous Au.

Project description:The catalytic properties of nanostructured Au and their physical origin were investigated by using the low-temperature CO oxidation as a test reaction. In order to distinguish between structural effects (structure-activity correlations) and bimetallic/bifunctional effects, unsupported nanoporous gold (NPG) samples prepared from different Au alloys (AuAg, AuCu) by selective leaching of a less noble metal (Ag, Cu) were employed, whose structure (surface area, ligament size) as well as their residual amount of the second metal were systematically varied by applying different potentials for dealloying. The structural and chemical properties before and after 1000 min reaction were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The catalytic behavior was evaluated by kinetic measurements in a conventional microreactor and by dynamic measurements in a temporal analysis of products (TAP) reactor. The data reveal a clear influence of the surface contents of residual Ag and Cu species on both O2 activation and catalytic activity, while correlations between activity and structural parameters such as surface area or ligament/crystallite size are less evident. Consequences for the mechanistic understanding and the role of the nanostructure in these NPG catalysts are discussed.

| S-EPMC3596058 | biostudies-literature

Surface Segregation in CuNi Nanoparticle Catalysts During CO<sub>2</sub> Hydrogenation: The Role of CO in the Reactant Mixture.

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| S-EPMC6453022 | biostudies-literature

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| S-EPMC7756314 | biostudies-literature

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| S-EPMC6099385 | biostudies-literature

Dynamics of Pd Dopant Atoms inside Au Nanoclusters during Catalytic CO Oxidation.

Project description:Doping gold nanoclusters with palladium has been reported to increase their catalytic activity and stability. PdAu24 nanoclusters, with the Pd dopant atom located at the center of the Au cluster core, were supported on titania and applied in catalytic CO oxidation, showing significantly higher activity than supported monometallic Au25 nanoclusters. After pretreatment, operando DRIFTS spectroscopy detected CO adsorbed on Pd during CO oxidation, indicating migration of the Pd dopant atom from the Au cluster core to the cluster surface. Increasing the number of Pd dopant atoms in the Au structure led to incorporation of Pd mostly in the S-(M-S) n protecting staples, as evidenced by in situ XAFS. A combination of oxidative and reductive thermal pretreatment resulted in the formation of isolated Pd surface sites within the Au surface. The combined analysis of in situ XAFS, operando DRIFTS, and ex situ XPS thus revealed the structural evolution of bimetallic PdAu nanoclusters, yielding a Pd single-site catalyst of 2.7 nm average particle size with improved CO oxidation activity.

| S-EPMC7604939 | biostudies-literature

Effect of the Electronic State of Cu, Ag, and Au on Diesel Soot Abatement: Performance of Cu/ZnO, Ag/ZnO, and Au/ZnO Catalysts.

Project description:Noble metals such as Au, Ag, and Cu supported over semiconducting ZnO are well-known heterogeneous oxidation catalysts. All of them have been utilized for the oxidation of diesel soot with varied success. However, Au-supported ZnO is seen to be superior among them. Here, we present a comparative study of all these three catalysts for diesel soot oxidation to explain why Au/ZnO is the best among them, demonstrating the contribution of electronic states of metals in composite catalysts. The electronic states of Cu, Ag, and Au determined by X-ray photoelectron spectroscopy on 1 wt % Cu/ZnO, 1 wt % Ag/ZnO, and 1 wt % Au/ZnO catalysts were correlated with their diesel soot oxidation activities. Although all three catalysts present reasonable diesel soot oxidation activities at relatively low temperature, 1% Cu/ZnO and 1% Ag/ZnO oxidize only about 60% of the deposited diesel soot around 250 °C and 1% Au/ZnO oxidizes 100% of the deposited diesel soot, at a temperature as low as 230 °C. The activity of the catalysts is attributed to the formation of stable M0-Mδ+ bifunctional catalytic sites at the metal-ZnO interface, which enhances the contact efficiency of solid diesel soot on Mδ+ and generates the superoxide species on M0 moieties. The stability of the bifunctional M0-Mδ+ sites is controlled by the electronic interactions between the metal (M) and n-type semiconductor ZnO at their interface. Very high activity of 1% Au/ZnO is attributed to the presence of Au3+ at the catalyst surface, which generates a stronger Coulombic force with diesel soot electrons. We demonstrate a direct relation between the diesel soot oxidation activity of these three metals and their electronic states at the catalyst surface.

| S-EPMC6648296 | biostudies-literature

A Rational Design of the Sintering-Resistant Au-CeO₂ Nanoparticles Catalysts for CO Oxidation: The Influence of H₂ Pretreatments.

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| S-EPMC6213528 | biostudies-literature

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| S-EPMC3200542 | biostudies-literature

Au/Ag/Cu-Mixed Catalysts for the Eco-Friendly Oxidation of 5-Hydroxymethylfurfural and Related Compounds to Carboxylic Acids under Atmospheric Oxygen in Water.

Project description:A green method for the oxidation of alcohols to carboxylic acids was developed using a novel co-catalytic system based on gold, silver, and copper catalysts. This reaction system was conducted under atmospheric oxygen in water and mild conditions to selectively oxidize 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid, as a building block for polyethylene furanoate, which is a 100% bio-based, future alternative to the petroleum-based polyethylene terephthalate. Furthermore, various primary alcohols were conveniently oxidized to their corresponding carboxylic acids in up to quantitative yields.

| S-EPMC7841932 | biostudies-literature

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