Oxygen and nitrogen interaction with rhodium single crystal surfaces

Comelli, G.; Dhanak, V.R.; Кискинова, М.; Prince, Kevin C.; Rosei, R.

doi:10.1016/s0167-5729(98)00003-x

Cited by 130 publications

(150 citation statements)

References 174 publications

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“…4 The overlayer structure of adsorbed atomic nitrogen on Rh͑111͒ was studied with scanning tunneling microscopy ͑STM͒. 5 For a detailed review of O and N chemistry on Rh͑111͒ and other single-crystal rhodium facets, see Comelli et al 6 The structures formed by adsorbed sulfur on Rh͑111͒ have been studied by LEED ͑Refs. 7 and 8͒ and STM ͑Ref.…”

Section: Introductionmentioning

confidence: 99%

Atomic and molecular adsorption on Rh(111)

Mavrikakis¹,

Rempel

Greeley³

et al. 2002

The Journal of Chemical Physics

202

161

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A systematic study of the chemisorption of both atomic ͑H, O, N, S, C͒, molecular (N 2 , CO, NO), and radical (CH 3 , OH) species on Rh͑111͒ has been performed. Self-consistent, periodic, density functional theory ͑DFT-GGA͒ calculations, using both PW91 and RPBE functionals, have been employed to determine preferred binding sites, detailed chemisorption structures, binding energies, and the effects of surface relaxation for each one of the considered species at a surface coverage of 0.25 ML. The thermochemical results indicate the following order in the binding energies from the least to the most strongly bound: N 2 ϽCH 3 ϽCOϽNOϽHϽOHϽOϽNϽSϽC. A preference for threefold sites for the atomic adsorbates is observed. Molecular adsorbates, in contrast, favor top sites with the exceptions of NO ͑hcp͒ and OH ͑fcc or bridge tilted͒. Surface relaxation leads to insignificant changes in binding energies but to considerable changes in the spacing between surface rhodium atoms, particularly for on-top adsorption where the rhodium atom directly below the adsorbate is lifted above the plane of the surface. RPBE binding energies are found to be in remarkable agreement with the available experimental values. All atomic adsorbates, except for H, have a significant diffusion barrier ͓between 0.4 and 0.6 eV ͑RPBE͔͒ on Rh͑111͒. Atomic H and molecular/radical adsorbates appear to be much more mobile on Rh͑111͒, with an estimated diffusion barrier between 0.1 and 0.2 eV ͑RPBE͒. Finally, the thermochemistry for dissociation of CO, NO, and N 2 on Rh͑111͒ has been examined. In all three cases, decomposition is found to be thermodynamically preferable to desorption.

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Section: Introductionmentioning

confidence: 99%

Atomic and molecular adsorption on Rh(111)

Mavrikakis¹,

Rempel

Greeley³

et al. 2002

The Journal of Chemical Physics

202

161

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“…26,27 Sharp changes in the LEED spot intensity were found at approximately the kinetic transition ͑KT͒ around P CO / P N 2 O = 1. The well-known ͑2 ϫ 2͒p2mg-O structure appeared at low P CO and its LEED intensity was fairly constant below KT.…”

Section: A General Features Of the Steady-state N 2 O Reductionmentioning

confidence: 97%

“…26,27 At temperatures between 125 and 300 K, the ͑2 ϫ 1͒p2mg LEED pattern appears sharply at saturation. This has been recently analyzed by scanning tunneling microscopy ͑STM͒ to be due to the zigzag oxygen chains decorating adjacent ͓110͔ Rh rows on unreconstructed ͑1 ϫ 1͒.…”

Section: A Surface Structuresmentioning

confidence: 99%

The collimation angle shift of desorbing product N2 in a steady-state N2O+CO reaction on Rh(110)

Matsushima

Nakagoe

Shobatake

et al. 2006

The Journal of Chemical Physics

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The angular distribution of desorbing product N 2 was studied in N 2 O decompositions on Rh͑110͒ in the temperature range of 60-700 K. The N 2 desorption collimates along 62°-68°off normal toward either the ͓001͔ or ͓001͔ direction in a transient N 2 O decomposition below ca. 470 K or in the steady-state N 2 O + CO reaction above 540 K. In the steady-state reaction at the temperature from ca. 470 to 540 K, however, the collimation angle shifts from 62°to 45°with decreasing surface temperature. This angle shift is ascribed to the steric hindrance by coadsorbed CO because the N 2 collimation in transient N 2 O decomposition at around 65°is recovered in the range of 380-500 K by an abrupt CO pressure drop followed by the decrease in CO coverage. N 2 O is oriented along the ͓001͔ direction before dissociation. A scattering model of the nascent N 2 by adsorbed CO is proposed, yielding smaller collimation angles.

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“…Particularly the sharp drop after reaching a coverage of about 0.5 ML at Ru(0001) and Rh(111) leads to an apparent uptake saturation, when employing low gas exposures as typical for many early ultra-high vacuum (UHV) surface science studies. 12,13,14 DFT calculations predicted, however, that much higher coverages should still be possible 15,16,17 , and Fig. 2 shows such data for some selected adsorbate configurations spanning the whole coverage range up to 1 ML 18 .…”

Section: A Formation Of Adlayersmentioning

confidence: 98%

Nanometer and Subnanometer Thin Oxide Films at Surfaces of Late Transition Metals

Reuter

2007

Nanocatalysis

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If metal surfaces are exposed to sufficiently oxygen-rich environments, oxides start to form. Important steps in this process are the dissociative adsorption of oxygen at the surface, the incorporation of O atoms into the surface, the formation of a thin oxidic overlayer and the growth of the once formed oxide film. For the oxidation process of late transition metals (TM), recent experimental and theoretical studies provided a quite intriguing atomic-scale insight: The formed initial oxidic overlayers are not merely few atomic-layer thin versions of the known bulk oxides, but can exhibit structural and electronic properties that are quite distinct to the surfaces of both the corresponding bulk metals and bulk oxides. If such nanometer or even sub-nanometer surface oxide films are stabilized in applications, new functionalities not scalable from the known bulk materials could correspondingly arise. This can be particularly important for oxidation catalysis, where technologically relevant gas phase conditions are typically quite oxygen-rich. In such environments surface oxides may even form naturally in the induction period, and actuate then the reactive steady-state behavior that has traditionally been ascribed to the metal substrates. Corresponding aspects are reviewed by focusing on recent progress in the modeling and understanding of the oxidation behavior of late TMs, using particularly the late 4d series from Ru to Ag to discuss trends.

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Oxygen and nitrogen interaction with rhodium single crystal surfaces

Cited by 130 publications

References 174 publications

Atomic and molecular adsorption on Rh(111)

Atomic and molecular adsorption on Rh(111)

The collimation angle shift of desorbing product N2 in a steady-state N2O+CO reaction on Rh(110)

Nanometer and Subnanometer Thin Oxide Films at Surfaces of Late Transition Metals

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