Adsorption of Simple Alkenes on Pt(111) and Pt−Sn Surface Alloys: Bond Strength versus Heat of Adsorption

Becker, Conrad; Haubrich, Jan; Wandelt, K.; Delbecq, Françoise; Loffreda, David; Sautet, Philippe

doi:10.1021/jp805089z

Cited by 25 publications

(21 citation statements)

References 14 publications

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“…The notations used in this work for π-and di-σ-bonding are consistent with the nomenclature reported in the literature for ethylene adsorption on noble metals. 34,35,39,40 3.1.3. Effect of vdW in C 2 H 4 Binding to Metal Carbides.…”

Section: Resultsmentioning

confidence: 99%

Systematic Theoretical Study of Ethylene Adsorption on δ-MoC(001), TiC(001), and ZrC(001) Surfaces

et al. 2016

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A systematic study of ethylene adsorption over δ-MoC(001), TiC(001), and ZrC(001) surfaces was conducted by means of calculations based on periodic density functional theory. The structure and electronic properties of each carbide pristine surface had a strong influence in the bonding of ethylene. It was found that the metal and carbon sites of the carbide could participate in the adsorption process. As a consequence of this, very different bonding mechanisms were seen on δ-MoC(001) and TiC(001). The bonding of the molecule on the TMC(001) systems showed only minor similarities to the type of bonding found on a typical metal like Pt(111). In general, the ethylene binding energy follow the trend in stability: ZrC(001) < TiC(001) < δ-MoC(001) < Pt(111). The van der Waals correction to the energy produces large binding energy values, modifies the stability orders and drives the ethylene closer to the surface but the adsorbate geometry parameters remain unchanged. Ethylene was activated on clearly defined binding geometries, changing its hybridization from sp 2 to sp 3 with an elongation (0.16−0.31 Å) of the CC bond. On the basis of this theoretical study, δ-MoC(001) is proposed as a potential catalyst for the hydrogenation of olefins, whereas TiC(001) could be useful for their hydrogenolysis.

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Section: Resultsmentioning

confidence: 99%

Systematic Theoretical Study of Ethylene Adsorption on δ-MoC(001), TiC(001), and ZrC(001) Surfaces

et al. 2016

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“…We have shown in previous studies that Sn is unable to bind with H or with the unsaturated molecule but promotes a partial electron transfer towards Pt. 17,18 That electron enrichment leads to a weakening of the interaction between the Pt sites and both butadiene and hydrogen and opens selective pathways for butadiene hydrogenation. 19 The influence of the Pt-Sn surface alloy on the coadsorption of the reactants at realistic H coverage was, however, not addressed from the computational viewpoint.…”

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Coadsorption of Butadiene and Hydrogen on the (111) Surfaces of Pt and Pt₂Sn Surface Alloy: Understanding the Cohabitation from First-Principles Calculations

Gautier

Sautet

2017

J. Phys. Chem. C

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Co-adsorption is a key initial step in heterogeneous catalysis, which by bringing the reactants together at high coverage on the surface of the catalyst has a clear implication on the catalytic reaction activity. We show that when using Density Functional Theory (DFT) calculations, the choice of the exchange correlation functional can have a qualitative influence on the nature of the obtained most stable coadsorption state. The coadsorption of butadiene and hydrogen, the precursor state for catalytic hydrogenation, is studied on Pt(111) and on the surface alloy Pt2Sn/Pt(111). At typical hydrogenation conditions, the PBE exchange correlation functional gives as most stable situation on both model catalysts a surface fully covered with hydrogen, butadiene remaining in gas phase. This behavior does not agree with available experimental data, and results from an incorrect balance between H and butadiene adsorption energy, mainly by a poor description of dispersion energy for butadiene adsorption. The non-local optPBE-vdW functional provides opposite and correct results, with a co-adsorption of butadiene and hydrogen as most stable situation. The butadiene adsorption energy is strengthened by the description of dispersive forces, hence modifying the nature of the energetic competition between the two adsorbates. The co-asorption energy difference between PBE and optPBE-vdW amounts to 1.04 (resp. 0.7) eV for Pt(111) (resp. Pt2Sn/Pt(111)) on the considered 3x3 unit cell. The computational study of co-adsorption systems from DFT is hence delicate. Errors do not only impact the quantitative adsorption energy of one adsorbate, but they might cumulate over several species, finally providing a qualitatively wrong picture of the optimal coadsorption situation. Going beyond the standard Generalized Gradient Approximation hence appears mandatory for a correct description of catalytic reactivity of unsaturated hydrocarbons.

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“…For the semi-hydrogenation of butadiene, the activities of its p(2 × 2) or ( √ 3 × √ 3) surfaces were found to be one order of magnitude lower than that of Pt(111) but the selectivity into butenes is largely increased by comparison to pure Pt (98-100%) [83]. Theoretical studies on surface alloys showed that the presence of Sn at the surface weakens the chemisorption of unsaturated hydrocarbon molecules [84]. More complex intermetallics -as least when evaluated with the number of atoms in the cell -were also identified as potential catalysts for selective semi-hydrogenation reactions (Fig.…”

Section: Pd-and Pt-based Intermetallic Catalystsmentioning

confidence: 99%

Ultra-Thin Films on Complex Metallic Alloy Surfaces: A Perspective

Fournée

Ledieu

Gaudry

et al. 2020

Recent Advances in Thin Films

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Complex metallic alloys (CMAs) may be defined as those intermetallic compounds having large (>≈nm) unit cell dimensions. This includes quasicrystals as a special case, the unit cell being infinite. The discovery of quasicrystals motivated the study of CMAs, and the surface science community became active in the field once stable samples of sufficient size were produced. While the initial surface science activity centred on clean surface preparation, increasingly the formation of thin films, both metallic and molecular grew in importance. In this chapter we give a brief introduction to this topic, and then focus on several current areas of interest. These include the growth and characterisation of ultrathin metallic films of diverse architectures, the formation through deposition of novel molecular overlayers and thin films, complex intermetallics as surface alloys, and the potential use of intermetallic surfaces for catalytic reactions.

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Adsorption of Simple Alkenes on Pt(111) and Pt−Sn Surface Alloys: Bond Strength versus Heat of Adsorption

Cited by 25 publications

References 14 publications

Systematic Theoretical Study of Ethylene Adsorption on δ-MoC(001), TiC(001), and ZrC(001) Surfaces

Systematic Theoretical Study of Ethylene Adsorption on δ-MoC(001), TiC(001), and ZrC(001) Surfaces

Coadsorption of Butadiene and Hydrogen on the (111) Surfaces of Pt and Pt₂Sn Surface Alloy: Understanding the Cohabitation from First-Principles Calculations

Ultra-Thin Films on Complex Metallic Alloy Surfaces: A Perspective

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Adsorption of Simple Alkenes on Pt(111) and Pt−Sn Surface Alloys: Bond Strength versus Heat of Adsorption

Cited by 25 publications

References 14 publications

Systematic Theoretical Study of Ethylene Adsorption on δ-MoC(001), TiC(001), and ZrC(001) Surfaces

Systematic Theoretical Study of Ethylene Adsorption on δ-MoC(001), TiC(001), and ZrC(001) Surfaces

Coadsorption of Butadiene and Hydrogen on the (111) Surfaces of Pt and Pt2Sn Surface Alloy: Understanding the Cohabitation from First-Principles Calculations

Ultra-Thin Films on Complex Metallic Alloy Surfaces: A Perspective

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Product

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Coadsorption of Butadiene and Hydrogen on the (111) Surfaces of Pt and Pt₂Sn Surface Alloy: Understanding the Cohabitation from First-Principles Calculations