Water Activated by Atomic Oxygen on Au(111) to Oxidize CO at Low Temperatures

Kim, Tae S.; Gong, Jinlong; Ojifinni, Rotimi A.; White, John; Mullins, C. Buddie

doi:10.1021/ja058263m

Cited by 108 publications

(130 citation statements)

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“…[11][12][13] Here we present experimental evidence with supporting density functional theory (DFT) calculations of carbonate formation and decomposition from the adsorption of oxygen-labeled carbon dioxide (C 18 O 2 ) on an atomic oxygen ( 16 O) precovered Au(111) surface. We studied the effects of CO 2 exposure, surface temperature, and oxygen coverage on carbonate formation and decomposition and also estimated reaction probabilities (∼10 -3 -10 -4 ) and activation energies as a function of conditions.Our experiments were performed in a UHV chamber that has been described elsewhere, [14][15][16][17][18][19] but details specific to this study are briefly summarized here. The Au(111) single crystal sample is mounted to a tantalum plate that can be resistively heated and is in thermal contact with a liquid nitrogen bath.…”

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Carbonate Formation and Decomposition on Atomic Oxygen Precovered Au(111)

et al. 2008

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The carbonate formation and decomposition (CO 3 T CO 2 + O a ) reaction on gold is important from the point of view of lowtemperature CO oxidation. Carbonate formation has been proposed as a possible reaction intermediate in CO oxidation in several investigations of supported and unsupported gold clusters. [1][2][3][4] Therefore, an understanding of this reaction on Au(111) may provide additional insight. Carbonate formation and decomposition went undetected in previous studies on Au (110) 5 and Au(111). 6 However, a surface carbonate was readily formed when oxygen precovered Ag(110) was exposed to CO 2 at 300 K. [7][8][9][10] This surface carbonate decomposes to produce CO 2 at 485 K and the remaining oxygen atoms recombinatively desorbed at 590 K. [7][8][9][10] Owing to its similarity with silver, we would anticipate equally facile carbonate formation and decomposition reactions on gold. Similar reactions have also been reported on other surfaces. [11][12][13] Here we present experimental evidence with supporting density functional theory (DFT) calculations of carbonate formation and decomposition from the adsorption of oxygen-labeled carbon dioxide (C 18 O 2 ) on an atomic oxygen ( 16 O) precovered Au(111) surface. We studied the effects of CO 2 exposure, surface temperature, and oxygen coverage on carbonate formation and decomposition and also estimated reaction probabilities (∼10 -3 -10 -4 ) and activation energies as a function of conditions.Our experiments were performed in a UHV chamber that has been described elsewhere, [14][15][16][17][18][19] but details specific to this study are briefly summarized here. The Au(111) single crystal sample is mounted to a tantalum plate that can be resistively heated and is in thermal contact with a liquid nitrogen bath. Oxygen ( 16 O) atoms were deposited using a radio frequency (RF) plasma-jet source. 16 O but with no exposure to C 18 O 2 (due to natural isotopic abundance of 18 O). As expected, no surface-bound oxygen was lost during carbonate formation and decomposition, in agreement with previous studies. [8][9][10] Figure 1b shows the amount of mass 34 produced (from the spectra in Figure 1a) as a function of C 18 O 2 exposure.To further examine the role of preadsorbed atomic oxygen on carbonate formation, we varied the oxygen precoverage (0.18-2.1 ML) while keeping both C 18 O 2 exposure (30 L) and surface temperature (167 K) constant (Figure 2). Mass 34 production increases with increasing 16 O a coverage, likely because more reactive oxygen is accessible to C 18 O 2 on the surface. Similar results were obtained employing surface temperatures of 220 and 300 K. We estimated the reaction probability of carbonate formation assuming a statistical distribution 7 in the decomposition of the surface-bound carbonate 16 OC 18 O 2 and obtained values of ∼10 -3 -10 -4 (uncertainties of (50%). These small values are likely part of the reason why an earlier study on Au(111) 6 reported undetectable surface carbonate formation. An Arrhenius plot of the reaction probabili...

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“…Our experiments were performed in a UHV chamber that has been described elsewhere, [14][15][16][17][18][19] but details specific to this study are briefly summarized here. The Au(111) single crystal sample is mounted to a tantalum plate that can be resistively heated and is in thermal contact with a liquid nitrogen bath.…”

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Carbonate Formation and Decomposition on Atomic Oxygen Precovered Au(111)

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“…Diese Bedingung wird auch heute noch häufig bei hohen Reaktivitäten beobachtet. [3] Der Reaktionsmechanismus wurde viel später erst an Edelmetallen in allen Einzelheiten studiert und der zweifelsfreie Nachweis für den Langmuir-Hinshelwood-Mechanismus erbracht.…”

Section: Forschungsaspekte Der Co-oxidationunclassified

“…B. die selektive Epoxidierung von Alkenen. [3,38] [42] Die Bindung von Kr-Atomen in kleinen Goldclustern wurde im Detail theoretisch untersucht und wird im Folgenden erçrtert.…”

Section: Die Co-oxidation Als Sondenreaktionunclassified

Die CO‐Oxidation als Modellreaktion für heterogene Prozesse

et al. 2011

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Die CO‐Oxidation, obwohl eine scheinbar einfache chemische Reaktion, dient als ein Modell, welches die Vielfalt und Attraktivität der heterogenen Katalyse offenbart. Das Fritz‐Haber‐Institut ist ein Ort, an dem ein multidisziplinärer Forschungsansatz zum Studium einer solchen heterogenen Reaktion innerhalb eines Instituts entwickelt und umgesetzt werden kann. Dabei ist die Forschung am Institut primär durch Neugier getrieben, was sich auch in den fünf Abschnitten dieses Aufsatzes widerspiegelt. Wir nutzen dabei mikroskopische Konzepte, um die Wechselwirkung einfacher Moleküle mit wohldefinierten Materialien wie Clustern in der Gasphase oder festen Oberflächen zu untersuchen. Dieser Ansatz erfordert nicht selten die Entwicklung von neuen Methoden, Werkzeugen und Materialien zur Verifizierung dieser Konzepte, und dies ermöglicht eine methodologisch solide, breit aufgestellte Herangehensweise als ein Markenzeichen des Instituts.

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“…The metallic single crystal surface-metallic nanoparticle system is a reasonable candidate for monitoring the distribution of plasmonic hot spots. Compared with polycrystalline nanoparticles (NPs), gold single crystal plates (GSCPs), a kind of two-dimensional metallic material, which have large atomicallyat surfaces, are more suitable for the fabrication of theoretical models and hold a great promise in catalytic elds [18][19][20] due to the benign catalytic activities of gold for some crystal facedependent catalytic reactions. The chemical-synthesized GSCPs also replace expensive traditional single crystal electrodes, to a certain extent, to study molecular adsorption behaviors on single crystal surfaces.…”

Section: Introductionmentioning

confidence: 99%

Insights into the heterogeneous distribution of SERS effect in plasmonic hot spots between Au@SiO₂monolayer film and gold single crystal plates

Wei

Zhang

et al. 2017

RSC Adv.

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Plasmonic hot spots, capable of confining strong electromagnetic fields near metallic surfaces, are particularly essential to a variety of enhanced spectroscopic techniques. Understanding the electric field distributions in the hot spot plays a crucial role in controlling the fabrication of plasmonic nanostructures for a variety of plasmon-based applications. The investigation of plasmonic hot spots in metallic nanosystems has not been fully evaluated. Here, we develop a facile approach by experimental means for investigating the distribution of plasmonic hot spots in surface-enhanced Raman spectroscopy (SERS) based on the dual-probe strategy by coupling a p-mercaptobenzoic acid-embedded Au@SiO 2 ((AupMBA)@SiO 2 ) nanoparticle monolayer film with thiophenol-modified gold single crystal plates (TPGSCPs). We demonstrated, for the first time, the heterogeneous distribution of SERS effect in the gap between Au@SiO 2 monolayer film and GSCPs. As increasing the gap distance by changing the thickness of silica spacer, the SERS effect of the probe on the gold nanoparticles decayed with a slower rate than that of the other probe attached onto the GSCPs. It mainly originated from the difference of localized dielectric environments and curvatures. By deliberately controlling the silica shell thickness, the switchable plasmonic coupling effect can be achieved between "particle-particle" gap mode and "particle-surface" gap mode. The results reveal that the transfer effect is more evident for (Au-pMBA) @SiO 2 films with thinner silica shell thickness and for 785 nm illumination as excitation wavelength than 633 nm. Moreover, the introduction of NaOH solution to (Au-pMBA)@SiO 2 films leads to the transfer of the hot spots to the areas between neighboring nanoparticles again due to the removal and dissolution of silica shells. The understanding gained from our experimental observation provides keen insight into the plasmonic hot spots in coupled nanostructures, offering guidance for rational design of plasmonic substrates for ultrasensitive SERS detections.

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Water Activated by Atomic Oxygen on Au(111) to Oxidize CO at Low Temperatures

Cited by 108 publications

References 23 publications

Carbonate Formation and Decomposition on Atomic Oxygen Precovered Au(111)

Carbonate Formation and Decomposition on Atomic Oxygen Precovered Au(111)

Die CO‐Oxidation als Modellreaktion für heterogene Prozesse

Insights into the heterogeneous distribution of SERS effect in plasmonic hot spots between Au@SiO₂monolayer film and gold single crystal plates

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Water Activated by Atomic Oxygen on Au(111) to Oxidize CO at Low Temperatures

Cited by 108 publications

References 23 publications

Carbonate Formation and Decomposition on Atomic Oxygen Precovered Au(111)

Carbonate Formation and Decomposition on Atomic Oxygen Precovered Au(111)

Die CO‐Oxidation als Modellreaktion für heterogene Prozesse

Insights into the heterogeneous distribution of SERS effect in plasmonic hot spots between Au@SiO2monolayer film and gold single crystal plates

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Insights into the heterogeneous distribution of SERS effect in plasmonic hot spots between Au@SiO₂monolayer film and gold single crystal plates