Density Functional Study of Benzene Adsorption on Pt(111)

Saeys, Mark; Reyniers, Marie Françoise; Marin, Guy; Neurock, Matthew

doi:10.1021/jp0201231

Cited by 172 publications

(329 citation statements)

References 53 publications

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“…1). This result is consistent with previous periodic slab GGA calculations, [40][41][42][43][44] as well as low-energy electron diffraction (LEED) 45 and scanning tunneling microscopy (STM) 46 experiments. Moreover, the PES shows a corrugation of 1.33 eV for Bz/Pt(111) when using PBE + vdW surf .…”

Section: Resultssupporting

confidence: 92%

“…To demonstrate the differences in the adsorption mechanism, we explore the potential-energy surface (PES) for Bz on the Pt(111) and Au(111) surfaces. We place a single Bz molecule at the eight high-symmetry adsorption sites of the (111) metal surface, 40 followed by geometry relaxation. The adsorption geometries and energies for Bz on Au(111) and Pt(111) at the preferable adsorption site are shown in Fig.…”

Section: Resultsmentioning

confidence: 99%

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Benzene adsorbed on metals: Concerted effect of covalency and van der Waals bonding

et al. 2012

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The adsorption of aromatic molecules on metal surfaces plays a key role in condensed matter physics and functional materials. Depending on the strength of the interaction between the molecule and the surface, the binding is typically classified as either physisorption or chemisorption. Van der Waals (vdW) interactions contribute significantly to the binding in physisorbed systems, but the role of the vdW energy in chemisorbed systems remains unclear. Here we study the interaction of benzene with the (111) surface of transition metals, ranging from weak adsorption (Ag and Au) to strong adsorption (Pt, Pd, Ir, and Rh). When vdW interactions are accurately accounted for, the barrier to adsorption predicted by standard density-functional theory (DFT) calculations essentially vanishes, producing a metastable precursor state on Pt and Ir surfaces. Notably, vdW forces contribute more to the binding of covalently bonded benzene than they do when benzene is physisorbed.Comparison to experimental data demonstrates that some of the recently developed methods for including vdW interactions in DFT allow quantitative treatment of both weakly and strongly adsorbed aromatic molecules on metal surfaces, extending the already excellent performance found for molecules in the gas phase.

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Section: Resultssupporting

confidence: 92%

Section: Resultsmentioning

confidence: 99%

Benzene adsorbed on metals: Concerted effect of covalency and van der Waals bonding

et al. 2012

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“…The horizontal bars show further computed benzene adsorption energies. [28][29][30][31] terraces on Cu(111), 36 we attribute this to step edges. We conclude that the adsorption heat on steps (g331 kJ/mol) is >10% higher than the initial adsorption heat on terrace sites (∼300 kJ/mol).…”

Section: Discussionmentioning

confidence: 99%

Heat of Adsorption of Naphthalene on Pt(111) Measured by Adsorption Calorimetry

et al. 2006

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The heat of adsorption of naphthalene on Pt(111) at 300 K was measured with single-crystal adsorption calorimetry. The heat of adsorption on the ideal, defect-free surface is estimated to be (300 -34Θ -199Θ 2 ) kJ/mol. From this, a C-Pt bond energy for aromatic hydrocarbons on Pt(111) of ∼30 kJ/mol is estimated, consistent with earlier results for benzene on Pt(111). There is higher heat of adsorption at very low coverage, attributed to step sites where the adsorption heat is g330 kJ/mol. Saturation coverage, Θ ) 1 ML, corresponds to 1.55 × 10 14 molecules/cm 2 . Sticking probability measurements of naphthalene on Pt (111) give a high initial value of 1.0 and a Kisliuk-type coverage dependence that implies precursor-mediated sticking. The ratio of the hopping rate to the desorption rate of this precursor is ∼51. Naphthalene adsorbs transiently on top of chemisorbed naphthalene molecules with a heat of adsorption of 83-87 kJ/mol.

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“…The interactions of benzene with the Pt(111) surface have been thoroughly studied using a variety of surface science techniques [18][19][20][21][22][23][24][25][26]. Based on these characterizations, benzene pi-bonds to Pt(111) with the ring parallel to the plane of the surface [18,20,22].…”

Section: Introductionmentioning

confidence: 99%

“…The chemisorbed benzene layer consists of two states, which are desorbed with activation energies of 82-88 kJ/mol and 117-129 kJ/mol over the 280-520 K temperature range [19,21,24]. More recently DFT calculations have determined the most preferred site for benzene adsorption on the Pt(111) surface is the bridge site, which is occupied first during adsorption, while at higher coverages a threefold hollow site is occupied [26]. Investigations of benzene oxidation on the Pt(111) surface have been limited, however.…”

Section: Introductionmentioning

confidence: 99%

Effect of Coadsorbed Water on Deep Oxidation Mechanisms: Temperature-Programmed Reactions of Benzene and Hydroxyl on the Pt(111) Surface

Marsh

Gland

2004

Catalysis Letters

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The deep oxidation of benzene by preadsorbed hydroxyl on the Pt(111) surface has been characterized using temperatureprogrammed reaction spectroscopy. A mechanism for benzene oxidation in the presence of coadsorbed water has been developed based on these experiments. Reaction-limited carbon dioxide and water are formed over the temperature range 330-530 K, indicating oxydehydrogenation and skeletal oxidation are occurring over this temperature range. Oxidation of benzene has been compared on the oxygen-covered Pt(111) surface with and without coadsorbed water. With preadsorbed hydroxyl, the yield of water at low-temperatures is increased, and the yield of carbon dioxide is increased. The temperature ranges for carbon dioxide and water formation above 300 K are increased by 30 K when water is coadsorbed with atomic oxygen to form hydroxyl. These results clearly suggest that hydroxyl enhances oxydehydrogenation below 300 K, which results in the formation of different dehydrogenated intermediates with increased activation energy for oxidation during the reaction. Taken together these kinetic and mechanistic results provide a clear description of the reactivity of hydroxyl during benzene deep oxidation on the Pt(111) surface.

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Density Functional Study of Benzene Adsorption on Pt(111)

Cited by 172 publications

References 53 publications

Benzene adsorbed on metals: Concerted effect of covalency and van der Waals bonding

Benzene adsorbed on metals: Concerted effect of covalency and van der Waals bonding

Heat of Adsorption of Naphthalene on Pt(111) Measured by Adsorption Calorimetry

Effect of Coadsorbed Water on Deep Oxidation Mechanisms: Temperature-Programmed Reactions of Benzene and Hydroxyl on the Pt(111) Surface

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