Dissociation of CO on Rh surfaces

Koster, de A; Santen, van Ra Rutger

doi:10.1016/0039-6028(90)90650-w

Cited by 64 publications

(28 citation statements)

References 77 publications

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“…27 This study permitted a qualitative description of the transition state for the surface dissociation and allowed a comparison of the activation barriers for dissociation along a number of different reaction paths. Dissociation follows a clear pattern.…”

Section: Introductionmentioning

confidence: 99%

Energetics and Dynamics for NO and CO Dissociation on Cu(100) and Cu(111)

Daelen

Newsam

et al. 1996

J. Phys. Chem.

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The dissociation of NO and CO has been studied on cluster models representing the copper(100) and -(111) single-crystal faces using density functional quantum calculations. For each surface, several possible reaction paths are proposed, for which we fully optimized the reactant, product, and transition states at the local density level (LDA). Nonlocal density functional calculations (NLDA) were then performed on these optimized geometries. The clusters we used, varying in size between 13 and 31 atoms, produced dissociation barriers and energies that were reasonably well converged with cluster size. Classical transition-state theory was used to calculate the rates of dissociation and recombination on the basis of computed frequencies of the predicted transition state and the reactant and product states. The transition states for NO and CO dissociation on all surfaces can be described as "tight" transition states corresponding to preexponentials for dissociation in the range 10 10 -10 13 s -1 . The dissociation barrier for NO is significantly lower than that for CO. In addition, the more open Cu(100) surface is more reactive toward dissociation than the close-packed Cu (111) surface. Nonlocal corrections to the LDA functional were found to have a small effect on dissociation barrier height, but the effect was found to be more profound on the recombination barrier and overall dissociation energies.

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Section: Introductionmentioning

confidence: 99%

Energetics and Dynamics for NO and CO Dissociation on Cu(100) and Cu(111)

Daelen

Newsam

et al. 1996

J. Phys. Chem.

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“…Using semi-empirical quantum chemical methods, the reaction paths for CO dissociation on Rh(111) and stepped Rh(111) have been analysed [10,11]. The activation energy for dissociation of CO on smooth Rh(111) was found to compete with CO desorption.…”

Section: Jc Baltzer Ag Science Publishersmentioning

confidence: 99%

“…Using the following values [7,10,14,35]: Earls(co)=-120 kJ/mol, Ef~ = -1020 kJ/mol, E~ ct = -150 kJ/mol, and E ads (O) = -400 kJ/mol, we deduce forEads(c) = --760 kJ/mol, whichisclosetothedatacalculatedinref. [11].…”

Section: The Langmuir-hinshelwood Mechanism Of Atomic C Oxidation On mentioning

confidence: 99%

Oxidation of carbidic carbon on a rhodium surface

et al. 1994

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Different mechanisms of atomic carbon and oxygen recombination on a rhodium surface are studied with Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). The kinetics of adsorbed carbidic carbon oxidation (carbon coverage 0c ~ 0.1-0.3 ML) by gas-phase oxygen that proceeds by a Langmuir-Hinshelwood reaction mechanism, provides the value of the activation energy for recombination (Ea: t g 170 -4-20 kJ/mol). Erae et depends slightly on the carbon coverage. An Eley-Rideal type of reaction was observed for adsorbed oxygen and atomic gas-phase carbon recombination which occurs in a dynamic regime. The low value found for the activation energy (near zero) is consistent with the mechanism that this exothermic reaction is too fast for energy dissipation into the substrate; the energy is mainly transferred into translational, vibrational and rotational energy of CO.

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“…In analogy with the results of theoretical calculations on the dissociation path of CO on rhodium by De Koster and van Santen [8], we visualize the rupture of the N-O bond as sketched in Fig. 8.…”

Section: No Dissociation On Rh(lll)mentioning

confidence: 99%

“…It should be noted, however, that the intramolecular bond weakening in the case of adsorbed CO is only modest, and that sufficient filling of the 2n* derived chemisorption levels occurs only when the molecule is in the transition state for dissociation. The latter can be envisaged as a state in which the molecule bends toward the surface, such that the overlap between metal d states and the 2n* levels is large [7,8]. The reader is referred to the literature for more thorough descriptions of chemisorption theory [7,[9][10][11][12][13][14].…”

Section: Qualitative Molecular Orbital Picture Of Dissociative Chemismentioning

confidence: 99%

Aspects of dissociative chemisorption and promotion in catalysis

Niemantsverdriet

1995

Applied Physics A: Materials Science & Processing

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Dissociation of CO on Rh surfaces

Cited by 64 publications

References 77 publications

Energetics and Dynamics for NO and CO Dissociation on Cu(100) and Cu(111)

Energetics and Dynamics for NO and CO Dissociation on Cu(100) and Cu(111)

Oxidation of carbidic carbon on a rhodium surface

Aspects of dissociative chemisorption and promotion in catalysis

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