Configurational correlations in the coverage dependent adsorption energies of oxygen atoms on late transition metal fcc(111) surfaces

Miller, Spencer D.; İnoğlu, Nilay; Kitchin, John R.

doi:10.1063/1.3561287

Cited by 68 publications

(71 citation statements)

References 74 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[30,31] With oxygen coverage increases, the width of the d-band also increases (Fig. 3), resulting from the increased overlap between the electron orbitals of the adsorbates and the surface metal atoms.…”

Section: Resultsmentioning

confidence: 93%

First‐principles calculations of oxygen adsorption on the Ti₃Al (0001) surface

Wei

Guo

Dai

et al. 2016

Surface & Interface Analysis

View full text Add to dashboard Cite

a Adsorption energies and density of states for O atoms adsorption on the Ti 3 Al (0001) surface have been calculated using first-principles calculations based on density functional theory. It is found that the order of O atom adsorption on the Ti 3 Al (0001) surface is associated with the adsorption energy as well as the distance of O atoms because of the interaction. The adsorption energy mainly depends on the bond number and bond strength between O and Ti atoms, and the adsorption site with rich-Ti surface (H I and HCP Al ) is first priority. The adsorption energy decreases with the increase of the oxygen coverage because of the characteristics of the valence d-orbitals of transition metals surface. Furthermore, the density of states indicates that the hybridization peak of O and Ti atoms is mainly from the contribution of Ti 3d-and O 2p-orbitals, and the hybridization peak of O and Al atoms from the contribution of Al 2p-and O 2p-orbitals.

show abstract

Section: Resultsmentioning

confidence: 93%

First‐principles calculations of oxygen adsorption on the Ti₃Al (0001) surface

Wei

Guo

Dai

et al. 2016

Surface & Interface Analysis

View full text Add to dashboard Cite

show abstract

“…Low energy electron diffraction (LEED) of the ordered ad-layer displays a diffraction pattern with a (2 × 2) periodicity. [23][24][25][26] Already early work interpreted the (2 × 2) LEED pattern to be the result of the superposition of three O-(2 × 1) superstructure domains consistent with a room temperature saturation coverage of 0.5 ML with respect to the Ir surface atom density. [23][24][25][26] Already early work interpreted the (2 × 2) LEED pattern to be the result of the superposition of three O-(2 × 1) superstructure domains consistent with a room temperature saturation coverage of 0.5 ML with respect to the Ir surface atom density.…”

Section: Introductionmentioning

confidence: 99%

“…[32][33][34] Oxygen binds strongly to the Ir(111) substrate with an energy gain of more than 4 eV per oxygen adatom (referred to the energy of a free oxygen atom) [23][24][25][26] and, because it is saturated by its strong bond to Ir, binds only weakly to Gr. [32][33][34] Oxygen binds strongly to the Ir(111) substrate with an energy gain of more than 4 eV per oxygen adatom (referred to the energy of a free oxygen atom) [23][24][25][26] and, because it is saturated by its strong bond to Ir, binds only weakly to Gr.…”

Section: Introductionmentioning

confidence: 99%

Oxygen orders differently under graphene: new superstructures on Ir(111)

et al. 2016

View full text Add to dashboard Cite

Using scanning tunneling microscopy, the oxygen adsorbate superstructures on bare Ir(111) are identified and compared to the ones formed by intercalation in between graphene and the Ir(111) substrate. For bare Ir(111) we observe O-(2 × 2) and O-(2 × 1) structures, thereby clarifying a persistent uncertainty about the existence of these structures and the role of defects for their stability. For the case of graphene-covered Ir(111), oxygen intercalation superstructures can be imaged through the graphene monolayer by choosing proper tunneling conditions. Depending on the pressure, temperature and duration of O2 exposure as well as on the graphene morphology, O-(2 × 2), O-(√3×√3)-R30°, O-(2 × 1) and O-(2√3 × 2√3)-R30° superstructures with respect to Ir(111) are observed under the graphene cover. Two of these structures, the O-(√3 × √3)-R30° and the (2√3 × 2√3)-R30° structure are only observed when the graphene layer is on top. Phase coexistence and formation conditions of the intercalation structures between graphene and Ir(111) are analyzed. The experimental results are compared to density functional theory calculations including dispersive forces. The existence of these phases under graphene and their absence on bare Ir(111) are discussed in terms of possible changes in the adsorbate-substrate interaction due to the presence of the graphene cover.

show abstract

“…Even at a metal surface that retains its integrity as it accumulates adsorbates, adsorbate-adsorbate interactions can cause large deviations from Langmuir behavior. 9 Adsorbates in close proximity tend to interact, leading to coverage-dependent binding energies, 8,[10][11][12] and activation energies sensitive to co-adsorbates. 13 Through-surface electronic effects, 14 surface strain, 12 and through-space electrostatics 15 are but a few of the many mechanisms by which adsorbates can interact.…”

mentioning

confidence: 99%

First-principles Thermodynamic Models in Heterogeneous Catalysis

Bray

Schneider

2013

Computational Catalysis

View full text Add to dashboard Cite

In this chapter we describe and demonstrate computational approaches to modeling surface adsorption, a process fundamental to all heterogeneous catalysts that takes into account surface structure, adsorbate–adsorbate interactions, and reaction conditions. We begin by describing the development of supercell density functional theory (DFT) models of adsorption at a surface, taking as an example O adsorption at the stepped and kinked Pt(321) surface. We then discuss how these DFT simulations can be used as a basis to parameterize a cluster expansion (CE) model, an Ising-type Hamiltonian that accounts for structural heterogeneity and for adsorbate–adsorbate interactions on a lattice. When converged, the DFT and CE models provide a self-consistent description of the ground states of the surface–adsorbate system. We present a detailed thermodynamic analysis of the system and describe how this can be used to extract equilibrium surface properties from the converged database and provide access to coverage-dependent adsorption energies and surface phase diagrams. Further, the CE enables Monte Carlo simulations of more extended surfaces under fixed temperature and chemical potential conditions, and the average properties from these simulations provide access to average coverages, heat capacities, and phase behavior. Finally, we describe how these same tools can be applied further to relate surface properties with reaction conditions and to describe surface kinetic processes such as diffusion or adsorption.

show abstract

Configurational correlations in the coverage dependent adsorption energies of oxygen atoms on late transition metal fcc(111) surfaces

Cited by 68 publications

References 74 publications

First‐principles calculations of oxygen adsorption on the Ti₃Al (0001) surface

First‐principles calculations of oxygen adsorption on the Ti₃Al (0001) surface

Oxygen orders differently under graphene: new superstructures on Ir(111)

First-principles Thermodynamic Models in Heterogeneous Catalysis

Contact Info

Product

Resources

About

Configurational correlations in the coverage dependent adsorption energies of oxygen atoms on late transition metal fcc(111) surfaces

Cited by 68 publications

References 74 publications

First‐principles calculations of oxygen adsorption on the Ti3Al (0001) surface

First‐principles calculations of oxygen adsorption on the Ti3Al (0001) surface

Oxygen orders differently under graphene: new superstructures on Ir(111)

First-principles Thermodynamic Models in Heterogeneous Catalysis

Contact Info

Product

Resources

About

First‐principles calculations of oxygen adsorption on the Ti₃Al (0001) surface

First‐principles calculations of oxygen adsorption on the Ti₃Al (0001) surface