The Influence of Promoters and Poisons on Carbon Monoxide Adsorption on Rh(100): A DFT Study

Nieskens, Davy L. S.; Ferré, Daniel Curulla; Niemantsverdriet, J.W.

doi:10.1002/cphc.200500082

Cited by 16 publications

(15 citation statements)

References 54 publications

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“…Van Bavel et al 1 found a nitrogen-CO lateral interaction energy of 19 kJ mol À1 . Theoretically, we have found in this study and in a former one 24 an interaction energy of 32 kJ mol À1 for carbon-CO and an interaction energy of 37 kJ mol À1 for nitrogen-CO. So, although DFT has not yet reached such a level of accuracy that a direct comparison with the values obtained from experiments is possible (possibly to some part due to the so-called 'overbinding effect' 47 ), we can still conclude that both experimentally as well as theoretically, the repulsive interaction between carbon and CO is less than between nitrogen and CO.…”

Section: Discussionsupporting

confidence: 66%

“…Recently, the effect of a wide range of coadsorbed atoms (covering the first three rows of the periodic table) on the strength and nature of the bond between CO and a Rh(100) surface has been investigated. 24 Following a similar approach as Van Bavel et al 1 we will use Temperature Programmed Desorption (TPD) to determine the effect of carbon on CO. This system is more complex than nitrogen and CO due to the presence of subsurface carbon atoms.…”

Section: Introductionmentioning

confidence: 99%

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The influence of carbon on the adsorption of CO on a Rh(100) single crystal

Nieskens

Jansen

Bavel

et al. 2006

Phys. Chem. Chem. Phys.

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The influence of carbon on the adsorption of CO from a Rh(100) single crystal has been studied by a combination of experimental techniques: Temperature Programmed Desorption (TPD), Low Energy Electron Diffraction (LEED), and High Resolution Electron Energy Loss Spectroscopy (HREELS). These experimental techniques were combined with a computational approach using Density Functional Theory (DFT). Using this combination of techniques, we have shown that surface carbon greatly influences adsorbed CO and we have determined the exact magnitude of this interaction. Furthermore, we have demonstrated that carbon does not remain fully on the surface; at higher coverage it diffuses partially to subsurface positions. The presence of these subsurface species significantly influences the adsorbates on the surface.

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Section: Discussionsupporting

confidence: 66%

Section: Introductionmentioning

confidence: 99%

The influence of carbon on the adsorption of CO on a Rh(100) single crystal

Nieskens

Jansen

Bavel

et al. 2006

Phys. Chem. Chem. Phys.

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“…The dehydrogenation of chemisorbed C 2 H 4 (a) layer on Pd(110) occurs above 450 K and forms the carbon-modified Pd(110) surface whose structure was found to depend sensitively on the substrate temperature . The presence of carbon species on metal surfaces strongly modify their catalytic performances in which, depending on its nature, the carbon species could act either as the poison or as the promoter. − To our knowledge, only few studies have been reported on the preparation of carbon-modified Co model surfaces. It was reported that heating the polycrystalline Co foil with chemisorbed C 2 H 4 (a) above 500 K caused the formation of surface carbide .…”

Section: Introductionmentioning

confidence: 99%

Surface Chemistry of C₂H₄, CO, and H₂ on Clean and Graphite Carbon-Modified Co(0001) Surfaces

Zhang

et al. 2011

J. Phys. Chem. C

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Chemisorption and surface reactions of C2H4, CO, and H2 on clean and graphite carbon-modified Co(0001) surfaces have been investigated by thermal desorption spectroscopy, X-ray photoelectron spectroscopy, and low-energy electron diffraction. The chemisorption and decomposition behaviors of C2H4 depend largely on the vacant sites available on clean Co(0001) at 130 K. C2H4 chemisorbs dissociatively to produce C2H2(a) and H(a) at low exposures but both dissociatively and molecularly to produce C2H4(a), C2H2(a), and H(a) at large exposures. Upon heating, some C2H4(a) desorbs and vacates surface sites, which results in the simultaneous decomposition of C2H4(a) into C2H3(a) and H(a). At 350 K, C2H3(a) either undergoes further dehydrogenation into C2H2(a) and H(a) or hydrogenates to produce C2H4. C2H2(a) then completely dehydrogenates to graphite carbon and H2 at 424 K. Graphite carbon modified Co(0001) surfaces were prepared by the thermal decomposition of C2H4 on clean Co(0001). The graphite carbon exerts both site-blocking effect and electronic effect on the reactivity of Co(0001) surface, suppressing the decomposition of C2H4(a) and weakening the interaction between the Co surface and CO(a) and H2(a). These results provide fundamental understandings of elementary steps of relevant heterogeneous catalytic reactions catalyzed by Co-based catalysts.

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“…The most prominent example of poisoning is the adsorption of CO on platinum and similar surfaces. [1][2][3] Another important issue is the co-adsorption of several species, which may have an important influence on dissociation processes. [3,4] More generally, the adsorption of small molecules from the environment can significantly modify the catalytic efficiency of such metal surfaces.…”

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confidence: 99%

Vibrational Frequencies of Water Adsorbed on (111) and (221) Nickel Surfaces from First Principle Calculations

2006

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Transition metal surfaces play a crucial role for many reactions in heterogeneous catalysis. Their catalytic functionality can be affected by a variety of factors, such as the morphology of the surface, defects, or poisoning. The most prominent example of poisoning is the adsorption of CO on platinum and similar surfaces. [1][2][3] Another important issue is the co-adsorption of several species, which may have an important influence on dissociation processes. [3,4] More generally, the adsorption of small molecules from the environment can significantly modify the catalytic efficiency of such metal surfaces. One particular case, in this scenario, is the adsorption of water. There are many theoretical and experimental studies of the structure and properties of water layers on metal surfaces in the literature. [5][6][7][8][9][10] Normally, the presence of a full layer is assumed in these investigations. However, the process of wetting, which is initiated by the adsorption of a single water molecule or small water clusters, is still poorly understood. From the view of an adsorbing water molecule, the surface has to compete thermodynamically with larger water clusters or simply the gas phase. Both phases provide a significantly larger entropic contribution to the free energy, which has to be compensated by a corresponding energy difference. Therefore, the theoretical investigation of the structural and energetic properties of the initial adsorption process on realistically modeled surfaces deserves particular attention.In particular, the crucial role of surface defects on adsorption processes is not always considered, especially in theoretical studies. Recently, we showed that a simple step defect on the nickel surface has the potential to enhance the adsorption energy of the initial water molecule by as much as 40 %. [11] Also the incremental adsorption energy of an additional second water molecule is higher than at a defect-free adsorption site. In principle, these adsorption energies can be determined experimentally, but spectroscopic parameters are often easier to obtain. First-principle calculations of experimentally accessible spectra are very scarce because of the relatively high computational cost involved in realistic and accurate calculations.Herein we want to bridge the gap between experiment and theory by providing ab initio calculations of IR peaks as a function of adsorption sites and cluster sizes, enabling for the first time a direct comparison of measurements and calculations. The initial steps of water adsorption on different nickel surfaces by means of their harmonic frequencies are characterized. The modification of the vibrational modes and frequencies of water clusters (monomer, dimer and trimer) upon adsorption are illustrated and these new vibrational modes involving the nickel-oxygen bond are described. Recent theoretical and experimental studies have shown that both the antisymmetric and the symmetric stretch vibrations can promote catalytic processes such as the chemisorption of methane on n...

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The Influence of Promoters and Poisons on Carbon Monoxide Adsorption on Rh(100): A DFT Study

Cited by 16 publications

References 54 publications

The influence of carbon on the adsorption of CO on a Rh(100) single crystal

The influence of carbon on the adsorption of CO on a Rh(100) single crystal

Surface Chemistry of C₂H₄, CO, and H₂ on Clean and Graphite Carbon-Modified Co(0001) Surfaces

Vibrational Frequencies of Water Adsorbed on (111) and (221) Nickel Surfaces from First Principle Calculations

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The Influence of Promoters and Poisons on Carbon Monoxide Adsorption on Rh(100): A DFT Study

Cited by 16 publications

References 54 publications

The influence of carbon on the adsorption of CO on a Rh(100) single crystal

The influence of carbon on the adsorption of CO on a Rh(100) single crystal

Surface Chemistry of C2H4, CO, and H2 on Clean and Graphite Carbon-Modified Co(0001) Surfaces

Vibrational Frequencies of Water Adsorbed on (111) and (221) Nickel Surfaces from First Principle Calculations

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Product

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Surface Chemistry of C₂H₄, CO, and H₂ on Clean and Graphite Carbon-Modified Co(0001) Surfaces