Interaction of Isophorone with Pd(111): A Combination of Infrared Reflection–Absorption Spectroscopy, Near-Edge X-ray Absorption Fine Structure, and Density Functional Theory Studies

Dostert, Karl‐Heinz; O’Brien, Casey P.; Riedel, Wiebke; Savara, Aditya; Liu, Wei; Oehzelt, Martin; Tkatchenko, Alexandre; Schauermann, Swetlana

doi:10.1021/jp506637v

Cited by 14 publications

(9 citation statements)

References 55 publications

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“…In our recent studies on hydrogenation of the simple carbonyl compounds acetophenone, acrolein, − and isophorone − over Pt and Pd surfaces, we demonstrated that the lateral interaction between neighboring adsorbates can crucially affect their adsorption geometry and chemical transformations. Particularly acetophenone was observed to form dimers on the Pt surface above 136 K, which can either be present as ketone–ketone species or undergo keto–enol tautomerization and form ketone–enol dimers .…”

Section: Introductionmentioning

confidence: 93%

Coverage-Dependent Adsorption Geometry of Acetophenone on Pt(111)

Attia

Schauermann

2019

J. Phys. Chem. C

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A microscopic-level understanding of the interaction of hydrocarbons with transition metal surfaces is an important prerequisite for rational design of new materials with improved catalytic properties. Particularly, their adsorption geometry might critically affect the ability of the surface to activate the selected chemical bonds. In this study, we investigate the interaction of a simple carbonyl compound acetophenone with Pt(111) single crystalline surface as a prototypical system. We apply a combination of molecular beam techniques with infrared reflection−absorption spectroscopy (IRAS) to address the adsorption geometry of acetophenone in a broad coverage range. In particular, we compare the IR spectra recorded for multilayer coverages, reflecting the molecular structure of largely unperturbed molecules, with the spectra obtained at submonolayer coverages, at which the molecular structure of acetophenone is perturbed by the interaction with the underlying metal. The acquired spectroscopic information suggests that two types of acetophenone surface species are formed and coexist on the surface at low temperature. At low coverages, the species S1 are populated, which adopt a flat-lying adsorption geometry with the benzene ring lying parallel to the surface plane. With increasing acetophenone coverage, a second type of the surface species appearsthe species S2exhibiting a more upright orientation with the benzene ring tilted away from the surface. The latter species are more weakly bound to the underlying metal substrate as compared to the flat-lying species S1 as indicated by the temperature dependence of their population on the surface. Additionally, we report a detailed assignment of the vibrational bands in acetophenone based on the comparison of the unperturbed molecular species accumulated in a multilayer with the spectra of gaseous acetophenone theoretically computed with the MP2/aug-cc-pVQZ-level of theory.

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Section: Introductionmentioning

confidence: 93%

Coverage-Dependent Adsorption Geometry of Acetophenone on Pt(111)

Attia

Schauermann

2019

J. Phys. Chem. C

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“…Higher partial pressures of the reactant have also been shown to enhance the selectivity towards C=O bond hydrogenation –. This effect was suggested to arise from increasing surface coverage, which causes the C=C group to become more tilted with respect to the surface and less vulnerable to attack by surface hydrogen atoms . The structure of the catalyst also critically influences the adsorption geometry of the reactant, and the selectivity of hydrogenation of α,β‐unsaturated ketones.…”

Section: Introductionmentioning

confidence: 97%

Selective Hydrogenation of Acrolein Over Pd Model Catalysts: Temperature and Particle‐Size Effects

O’Brien

Dostert

Schauermann

et al. 2016

Chemistry A European J

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In this work, the selectivity in hydrogenation of acrolein over Fe3O4-supported Pd nanoparticles is investigated as a function of nanoparticle size in the 220-270 K temperature range. While Pd(111) shows nearly 100% selectivity towards the desired hydrogenation of the C=O bond to produce propenol, Pd nanoparticles were found to be much less selective towards this product.In-situ detection of surface species using infrared-reflection absorption spectroscopy shows that the selectivity towards propenol critically depends on the formation of an oxopropyl spectator species. While an overlayer of oxopropyl species is effectively formed on Pd(111) turning the surface highly selective for propenol formation, this process is strongly hindered on Pd nanoparticles by acrolein decomposition resulting in CO formation. We show that the extent of acrolein decomposition can be tuned by varying the particle size and the reaction temperature.As a result, significant production of propenol is observed over 12 nm Pd nanoparticles at 250 K, while smaller (4 and 7 nm) nanoparticles did not produce propenol at any of the temperatures 2 investigated. The possible origin of particle size dependence of propenol formation is discussed.This work demonstrates that the selectivity in hydrogenation of acrolein is controlled by the relative rates of acrolein partial hydrogenation to oxopropyl surface species and of acrolein decomposition, which has significant implications for rational catalyst design.3

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“…therein) that incorporate vdW forces in DFT electronic structure calculations, either through novel exchange-correlation functionals or as additional potential terms in the Kohn-Sham Hamiltonian. In surface science, these methods have been rather successfully used in describing multilayer systems involving graphene and boron-nitride [23], organic molecules adsorbed on metal [24][25][26][27][28][29][30][31][32][33][34][35][36][37] and nonmetal surfaces [38][39][40], graphene adsorbed on metal surfaces [41][42][43], and even organic molecules adsorbed on graphene adsorbed on metal surfaces [44]. These vdW methods have also been used to study the interaction of polyatomic [45][46][47] and diatomic [48][49][50] molecules with surfaces, and even with aromatic systems [51].…”

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confidence: 99%

Role of van der Waals forces in the diffraction of noble gases from metal surfaces

et al. 2016

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The role of van der Waals (vdW) forces in the description of scattering processes of noble gases from metal surfaces is currently under debate. Although features of the potential energy surface such as anticorrugation or adsorption energies are sometimes found to be well described by standard density functional theory (DFT), the performance of DFT to describe diffraction spectra may rely on the accuracy of the vdW functionals used. To analyze the precise role of these vdW forces in noble gas diffraction by metal surfaces, we have thoroughly studied the case of Ne/Ru(0001), for which accurate experimental results are available. We have carried out classical and quantum dynamics calculations by using DFT-based potentials that account for the effect of vdW interactions at different levels of accuracy. From the comparison of our results with experimental data, we conclude that the inclusion of vdW effects is crucial to properly describe diffraction of noble gases from metal surfaces. We show that among the vdW-DFT functionals available in the literature, not all of them can be used to accurately describe this process. DOI: 10.1103/PhysRevB.93.060301The diffraction of noble gases is largely used in surface science as a nondestructive analytical tool to investigate, for example, surface morphology and surface phonons (see Refs. [1,2] and refs. therein). Furthermore, this tool can also be used to study the dynamics of adsorbate/surface systems [3,4]. In order to extract the maximum amount of information from experimental diffraction spectra, a detailed comparison with theoretical simulations is often desirable. However, from a theoretical point of view, the description of the electronic structure of noble-gas atom/surface systems, in particular when metal surfaces are involved, is not a trivial matter due to the possible prominent role of van der Waals (vdW) interactions. The first theoretical approach to treat these kind of systems was reported in the early 80's by Esbejerg and Nørskov [5], who proposed the use of an interaction potential proportional to the unperturbed electron density of the substrate at the position of the atomic projectile. But this approach was questioned only two years later by experimental results showing anticorrugation effects in He scattering from Ni(110) [6] that could not be reproduced with this simple model. Later on, in the 90's, first principles calculations were performed using a jellium model to describe the substrate [7,8]. Although this simple model is good enough to reproduce some general properties, to take into account the lattice structure is essential to analyze many other properties such as the corrugation amplitudes of the system, which are responsible for diffraction scattering phenomena.The periodic lattice structure of a noble-gas atom/surface system can be well described by density functional theory (DFT) with periodic boundary conditions. However, standard DFT functionals do not include, per se, the effect of the van * fernando.martin@uam.es † cristina.diaz@uam.es der W...

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Interaction of Isophorone with Pd(111): A Combination of Infrared Reflection–Absorption Spectroscopy, Near-Edge X-ray Absorption Fine Structure, and Density Functional Theory Studies

Cited by 14 publications

References 55 publications

Coverage-Dependent Adsorption Geometry of Acetophenone on Pt(111)

Coverage-Dependent Adsorption Geometry of Acetophenone on Pt(111)

Selective Hydrogenation of Acrolein Over Pd Model Catalysts: Temperature and Particle‐Size Effects

Role of van der Waals forces in the diffraction of noble gases from metal surfaces

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