Relating the coverage dependence of oxygen adsorption on Au and Pt fcc(111) surfaces through adsorbate-induced surface electronic structure effects

Miller, Spencer D.; Kitchin, John R.

doi:10.1016/j.susc.2009.01.021

Cited by 105 publications

(82 citation statements)

References 64 publications

(85 reference statements)

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“…Similar to previous studies by Miller and Kitchin of O adsorption on Pt(111) and Au(111) [27], and by Getman and Schneider of NO oxidation on Pt(111) [30], we find that the differential binding energy E diff (h) increases nearly linearly with coverage. However, in the limit of low coverages below the threshold coverage h°adsorbate-adsorbate interactions should be weak and therefore, we keep E diff (h) constant where there is no direct interaction and the adsorbates do not share any metal atoms.…”

Section: Methodssupporting

confidence: 90%

“…Theoretical models can be used to construct phase diagrams and predict surface conditions and the possibility of surface oxide or even bulk oxide formation [22][23][24][25] but in the end the state of the surface is a kinetic phenomenon as shown by Reuter et al [26]. Adsorbate-adsorbate interactions can have a significant effect on the energy of adsorption and desorption steps [27] and can alter the stability of transition states [15,28,29], and can therefore affect the catalytic rate substantially as shown recently by Schneider and coworkers [10,30,31]. The question therefore arises to what extend the state of the surface and in particular adsorbate-adsorbate interactions affect the trends in reactivity from one metal to the next.…”

Section: Introductionmentioning

confidence: 99%

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Understanding Trends in Catalytic Activity: The Effect of Adsorbate–Adsorbate Interactions for CO Oxidation Over Transition Metals

2010

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Using high temperature CO oxidation as the example, trends in the reactivity of transition metals are discussed on the basis of density functional theory (DFT) calculations. Volcano type relations between the catalytic rate and adsorption energies of important intermediates are introduced and the effect of adsorbate-adsorbate interaction on the trends is discussed. We find that adsorbateadsorbate interactions significantly increase the activity of strong binding metals (left side of the volcano) but the interactions do not change the relative activity of different metals and have a very small influence on the position of the top of the volcano, that is, on which metal is the best catalyst.

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Section: Methodssupporting

confidence: 90%

Section: Introductionmentioning

confidence: 99%

Understanding Trends in Catalytic Activity: The Effect of Adsorbate–Adsorbate Interactions for CO Oxidation Over Transition Metals

2010

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“…They found a nearly linear coverage dependence for the calculated adsorption energies of the most stable configurations for atomic oxygen on both surfaces [28].…”

Section: Oxygen Adsorptionmentioning

confidence: 97%

“…German and Efremenko [23] Miller and Kitchi [27][28] used DFT calculations to study adsorption of oxygen on Au and Pt (111) surfaces. They found a nearly linear coverage dependence for the calculated adsorption energies of the most stable configurations for atomic oxygen on both surfaces [28].…”

Section: Oxygen Adsorptionmentioning

confidence: 99%

Adsorption of small molecules on gold single crystal surfaces

Carabineiro

Nieuwenhuys

2009

Gold Bull

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Much more work has been carried out on supported gold catalysts (also called "real" catalysts) than on gold single crystal surfaces. However, for fundamental understanding of catalysis by gold, well-defined gold surfaces and controlled conditions using the surface science approach may provide useful information concerning reaction mechanisms and the nature of active centers. This paper presents a brief overview on the work carried out regarding adsorption of several small molecules on

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“…Several other groups have also investigated oxygen adsorption on gold using DFT; however, the possibility of gold release from the surface induced by adsorbed O was not considered [31,38,89,106,[130][131][132]. For example, Miller and Kitchin [130] calculated a surface free energy plot for different coverages and structures of oxygen on Au (111), but without considering structures involving Au extraction from the surface. Consideration of metal atom release is critical since changes in metal-metal bonding due to such added-metal structures will substantially affect bonding mechanisms and bond energies.…”

Section: Release Of Au Upon Adsorption Of Electronegative Elements Onmentioning

confidence: 99%

Insights from Theory on the Relationship Between Surface Reactivity and Gold Atom Release

2010

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Density functional theory, informed by experimental studies, is used to investigate the interplay of surface morphology, the adsorption site of reactants, the nature of the interaction between adsorbates and the surface, the potential energy landscape for adsorbates on the surface, adsorbate coverage, temperature, and the dynamic evolution of these factors during adsorption and reaction. We summarize our current understanding of Au atom release on the (111) surface and the corresponding effects on adsorption and reactivity. Gold was selected for these investigations because of the recent intense interest in the activity of gold nanoparticles for several important catalytic reactions. Fundamental experimental studies on Au single-crystal surfaces have established that atomic O is extremely active for oxidation of CO and olefins, that the local bonding of O is an important factor in determining the reactivity and selectivity for oxidation, and that Au atom release is induced by electronegative adsorbates, such as O, Cl, and S. These experimental results guided our theoretical studies. Density functional theory is an extremely useful tool since it evaluates the energetics associated with the incorporation of gold into the adsorbate layer, while providing fundamental physical insight into the underlying cause of gold incorporation. We use our results from static DFT calculations along with ab initio molecular dynamics simulations to understand the effect of surface morphology on the activity of gold for CO oxidation. Our investigation of Au atom release and incorporation induced by electronegative atoms clearly illustrates the importance of using experiments in combination with theory to establish the importance of and the underlying reasons for metal atom release and the affect on bonding and reactivity.

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Relating the coverage dependence of oxygen adsorption on Au and Pt fcc(111) surfaces through adsorbate-induced surface electronic structure effects

Cited by 105 publications

References 64 publications

Understanding Trends in Catalytic Activity: The Effect of Adsorbate–Adsorbate Interactions for CO Oxidation Over Transition Metals

Understanding Trends in Catalytic Activity: The Effect of Adsorbate–Adsorbate Interactions for CO Oxidation Over Transition Metals

Adsorption of small molecules on gold single crystal surfaces

Insights from Theory on the Relationship Between Surface Reactivity and Gold Atom Release

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