The Energy Dependence of the Ratio of Step and Terrace Reactivity for H<sub>2</sub> Dissociation on Stepped Platinum

Groot, Irene M. N.; Kleyn, Aart W.; Juurlink, Ludo B. F.

doi:10.1002/ange.201007093

Cited by 12 publications

(20 citation statements)

References 23 publications

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“…However, the QCT study overestimated the trapping-mediated contribution to the reaction at low E i , which was attributed to one mechanism operative for trapping in the classical calculations (excitation of the rotation) not being allowed in QD, as the trapping well should not support rotationally excited bound states for their PES. 17 H 2 + Pt(211) has also been studied experimentally by Groot et al 7,8,32 Their molecular beam sticking probabilities 7 were in reasonable agreement with the QD results for (ν = 0, j = 0) H 2 of Olsen et al, 17 although the QD results based on the BP functional overestimated the sticking at high E i . Likewise, there were discrepancies at low E i , with the computed trappingmediated contribution to the sticking being too low compared to the experimental result.…”

Section: Introductionsupporting

confidence: 65%

Transferability of the Specific Reaction Parameter Density Functional for H₂ + Pt(111) to H₂ + Pt(211)

et al. 2019

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The accurate description of heterogeneously catalyzed reactions may require chemically accurate evaluation of barriers for reactions of molecules at the edges of metal nanoparticles. It was recently shown that a semiempirical density functional describing the interaction of a molecule dissociating on a flat metal surface (CHD3 + Pt(111)) is transferable to the same molecule reacting on a stepped surface of the same metal (Pt(211)). However, validation of the method for additional systems is desirable. To address the question whether the specific reaction parameter (SRP) functional that describes H2 + Pt(111) with chemical accuracy is also capable of accurately describing H2 + Pt(211), we have performed molecular beam simulations with the quasi-classical trajectory (QCT) method, using the SRP functional developed for H2 + Pt(111). Our calculations used the Born–Oppenheimer static surface model. The accuracy of the QCT method was assessed by comparison with quantum dynamics results for reaction of the ro-vibrational ground state of H2. The theoretical results for sticking of H2 and D2 on Pt(211) are in quite good agreement with the experiment, but uncertainties remain because of a lack of accuracy of the QCT simulations at low incidence energies and possible inaccuracies in the reported experimental incidence energies at high energies. We also investigated the nonadiabatic effect of electron–hole pair excitation on the reactivity using the molecular dynamics with the electron friction (MDEF) method, employing the local density friction approximation (LDFA). Only small effects of electron–hole pair excitation on sticking are found.

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Section: Introductionsupporting

confidence: 65%

Transferability of the Specific Reaction Parameter Density Functional for H₂ + Pt(111) to H₂ + Pt(211)

et al. 2019

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“…At the lowest incident energy, normalEkin = 65 meV (blue), sticking is linearly dependent on position, hence step density, on both sides. This can only be accounted for by independent contributions of steps and terraces (31, 39, 40). The solid blue lines in Fig.…”

Section: Resultsmentioning

confidence: 99%

Steps on Pt stereodynamically filter sticking of O ₂

Cao

Lent

Kleyn

et al. 2019

Proc. Natl. Acad. Sci. U.S.A.

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Low coordinated sites on catalytic surfaces often enhance reactivity, but the underlying dynamical processes are poorly understood. Using two independent approaches, we investigate the reactivity of O2impinging onto platinum and resolve how step edges on (111) terraces enhance sticking. At low incident energy, the linear dependence on step density, independence of step type, and insensitivity to O2’s molecular alignment show that trapping into a physisorbed state precedes molecular chemisorption and dissociation. At higher impact energies, direct molecular chemisorption occurs in parallel on steps and terraces. While terraces are insensitive to alignment of the molecule within the (111) plane, steps favor molecules impacting with their internuclear axis parallel to the edge. Stereodynamical filtering thus controls sticking and dissociation of O2on Pt with a twofold role of steps.

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“… 47 , 48 Our results may imply that the dissociation of H 2 participates more strongly in the multistep dynamics than assumed so far because defects do not lead to lower barriers for hydrogen dissociation on copper. This may become particularly relevant for very small Cu particles, where a Wulff construction would not include t 2 type sites (small metal nanoparticles are octahedral in shape and have edge-like sites but not the t 2 bottom sites 14 ).…”

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Anomalous Dependence of the Reactivity on the Presence of Steps: Dissociation of D₂ on Cu(211)

Füchsel

Cao

et al. 2017

J. Phys. Chem. Lett.

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Stepped metal surfaces are usually assumed to exhibit an increased catalytic activity for bond cleavage of small molecules over their flat single-crystal counterparts. We present experimental and theoretical data on the dissociative adsorption of molecular hydrogen on copper that contradicts this notion. We observe hydrogen molecules to be more reactive on the flat Cu(111) than on the stepped Cu(211) surface. We suggest that this exceptional behavior is due to a geometric effect, that is, that bond cleavage on the flat surface does not occur preferentially over a top site.

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The Energy Dependence of the Ratio of Step and Terrace Reactivity for H₂ Dissociation on Stepped Platinum

Cited by 12 publications

References 23 publications

Transferability of the Specific Reaction Parameter Density Functional for H₂ + Pt(111) to H₂ + Pt(211)

Transferability of the Specific Reaction Parameter Density Functional for H₂ + Pt(111) to H₂ + Pt(211)

Steps on Pt stereodynamically filter sticking of O ₂

Anomalous Dependence of the Reactivity on the Presence of Steps: Dissociation of D₂ on Cu(211)

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The Energy Dependence of the Ratio of Step and Terrace Reactivity for H2 Dissociation on Stepped Platinum

Cited by 12 publications

References 23 publications

Transferability of the Specific Reaction Parameter Density Functional for H2 + Pt(111) to H2 + Pt(211)

Transferability of the Specific Reaction Parameter Density Functional for H2 + Pt(111) to H2 + Pt(211)

Steps on Pt stereodynamically filter sticking of O 2

Anomalous Dependence of the Reactivity on the Presence of Steps: Dissociation of D2 on Cu(211)

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The Energy Dependence of the Ratio of Step and Terrace Reactivity for H₂ Dissociation on Stepped Platinum

Transferability of the Specific Reaction Parameter Density Functional for H₂ + Pt(111) to H₂ + Pt(211)

Transferability of the Specific Reaction Parameter Density Functional for H₂ + Pt(111) to H₂ + Pt(211)

Steps on Pt stereodynamically filter sticking of O ₂

Anomalous Dependence of the Reactivity on the Presence of Steps: Dissociation of D₂ on Cu(211)