Determination of the adsorption geometry of ethylene on Ni{110} using photoelectron diffraction

Gießel, Tatjana; Terborg, Ralf; Schaff, Oliver; Lindsay, Robert; Baumgärtel, Peter; Hoeft, J.; Schindler, K.‐M.; Bao, Sheng; Theobald, Andreas; Fernandez, Vincent; Bradshaw, Alexander M.; Chrysostomou, Demetrius; McCabe, Thomas; Lloyd, D. R.; Davis, R. F.; Booth, Nicholas; Woodruff, D.P.

doi:10.1016/s0039-6028(99)00780-3

Cited by 9 publications

(5 citation statements)

References 31 publications

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“…The determination of adsorption sites of coadsorbed chemical species on single-crystal surfaces has been investigated by using several experimental techniques and theoretical models. − The knowledge of the geometrical arrangement of the reactants on the surface allows shedding the light on the step-by-step sequence of elementary reactions through which surface chemical species transform into other ones . Such investigations lead to more efficient industrial processes and to a reduction of production costs and wastes.…”

Section: Introductionmentioning

confidence: 99%

Vibrational Investigation of Catalyst Surfaces: Change of the Adsorption Site of CO Molecules upon Coadsorption

Politano

Chiarello

2011

J. Phys. Chem. C

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The understanding of the elementary steps occurring in catalytic reactions in the heterogeneous phase is one of the foremost goals of surface science. Adsorption on solid surfaces is the first step in catalytic reactions. Therefore, the individuation of adsorption sites for reactive chemical species is essential information to tailor catalytic properties of surfaces and interfaces. As a matter of fact, the change in adsorption site often implies a different reactivity for chemisorbed adsorbates and a selective catalytic activity. In this Feature Article, we evidence how vibrational spectroscopy can be used for individuating adsorption sites in coadsorption systems on catalyst surfaces. In particular, we studied CO coadsorption with oxygen, nitrogen, and hydrogen on the Ni(111) and the Ni(100) surfaces. Our attention was focused on the determination of CO adsorption sites in the various investigated systems. For CO adsorbed alone on the substrate, the preferential adsorption sites are the 3-fold hollow on the (111) face and the atop and bridge for the (100) surface. Striking changes in the CO adsorption site occur whenever CO is coadsorbed with other chemical species. In the CO + O coadsorption system, atop sites are populated by CO on the Ni(111) surface, while bridge and 4-fold hollow sites are occupied on Ni(100). In the CO + N phase on Ni(111), CO molecules occupy the bridge site of the pseudo-(100) reconstructed surface. For a H-precovered Ni(100) surface at 150 K, the CÀO stretching frequency is near its gas-phase value, thus suggesting the occurrence of a weakly bonded CO phase without changes of adsorption sites.

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Section: Introductionmentioning

confidence: 99%

Vibrational Investigation of Catalyst Surfaces: Change of the Adsorption Site of CO Molecules upon Coadsorption

Politano

Chiarello

2011

J. Phys. Chem. C

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“…17,20 The effect is due to the diffraction of locally generated photoelectrons by other atoms within the same adsorbed species: variation of the diffraction intensity with the photoelectron energy using synchrotron radiation provides structural information. 17,21,22 A major advance in technique has permitted the calorimetric determination of heats of adsorption of hydrocarbons on thin single-crystal surfaces of metals. 23,24 Films of about 200 nm thickness are grown epitaxially by vapour deposition on the surface of a sodium chloride crystal cut to expose the desired face; it is then dissolved in water, and the film, the surface of which mimics that of the crystal, is then rescued.…”

Section: Chaptermentioning

confidence: 99%

“…Moreover there are well-established chemisorbed structures that cannot be correlated with that of any conceivable organometallic complex. 21 r Minimally changed structures are found in complexes containing only one or two metal atoms (e.g. 4 EPtCl 3 − ; 4 EOs 2 (CO) 8 ), while triatomic complexes can accommodate dissociated species ( 3 ECo 3 (CO) 9 ): extended metal surfaces provide more ample opportunities for dissociation to occur, given the right conditions, and adsorption in the undissociated form is much more restricted.…”

Section: Chaptermentioning

confidence: 99%

“…Exceptions to this generalisation are rare, and are open to doubt. 21 The rules of chemical bonding apply equally to chemisorption, and we are therefore dealing with chemistry in two dimensions. In some cases, species occupy sites that might have been predicted using chemical common sense; it does not need refined theory to see that ethylidyne, wanting to form three σ bonds to the surface, will bond at trigonal sites on the fcc(111) plane (except, curiously, and inexplicably, on Ni (111), where it does not form), rather than elsewhere.…”

Section: Theoretical Approaches 1624165−167mentioning

confidence: 99%

“…(A) Ethene on Ni(111) by PED; 20,116 (b) ethene on Ni(110); 21 (C) ethyne on Ni(111) 21,50,147. involving frequencies and intensities; there is no attempt to define the exact location of the carbon atoms with respect to the lattice of metal atoms with which they are in contact.…”

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confidence: 99%

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The Chemisorption of Hydrocarbons

Metal-Catalysed Reactions of Hydrocarbons

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PREFACEWe have considered at some length the ways in which hydrogen can interact with metals and supported metal catalysts, and with itself when isotopic analogues are used, and because our main theme is the reactions that hydrogen undergoes with hydrocarbons it is logical that we should next examine how they interact with metal surfaces. The great variety of types of hydrocarbon (alkanes, alkenes, alkynes, aromatics etc.) make this potentially a much larger subject than that of the last Chapter, and a further complication is that the forms adopted by a specific hydrocarbon depend on the nature of the metal, the crystal plane, the particle size, and particularly the temperature. These factors have acted as a challenge to experimentalists and theoreticians, and there is a very extensive literature, on which it will be necessary to try to impose some order; selection and compression will also be called for.Our aim will be to try to identify those adsorbed species most likely to be intermediates in the reactions we shall meet later, and to recognise species derived from the original molecule that may inhibit the desired reaction, or indeed be required for reaction under more forcing conditions. In some cases the structure of the relevant intermediate looks like that of the product, and, just as with hydrogen, the essential part of the process is accomplished in the chemisorption. The very precise and detailed information available on the structures of certain adsorbed species and their effects on the arrangement of surface metal atoms will excite our admiration. 153 154 CHAPTER 4

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3.8.6 Adsorbate properties of linear hydrocarbons

Rupprechter¹,

Somorjai²

Adsorbed Layers on Surfaces. Part 5: Adsorption of Molecules on Metal, Semiconductor and Oxide Surfaces

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Determination of the adsorption geometry of ethylene on Ni{110} using photoelectron diffraction

Cited by 9 publications

References 31 publications

Vibrational Investigation of Catalyst Surfaces: Change of the Adsorption Site of CO Molecules upon Coadsorption

Vibrational Investigation of Catalyst Surfaces: Change of the Adsorption Site of CO Molecules upon Coadsorption

The Chemisorption of Hydrocarbons

3.8.6 Adsorbate properties of linear hydrocarbons

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