Ethylene epoxidation on Ag(110): The role of subsurface oxygen

Journal Article · Thu Aug 24 04:00:00 EDT 1989 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100354a038· OSTI ID:6985639

van den Hoek, P J ^[1]; Baerends, E J ^[2]; van Santen, R A ^[3]

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1. FOM Institute for Atomic and Molecular Physics, Amsterdam (Netherlands)
2. Free Univ. of Amsterdam (Netherlands)
3. Technical Univ. of Eindhoven (Netherlands)

The authors have performed electronic structure calculations on the chemisorption of atomic oxygen on Ag(110) and on the subsequent reaction of this chemisorbed oxygen with ethylene. These calculations show that the presence of subsurface oxygen (i) reduces the bond energy between silver and adsorbed oxygen and (ii) converts the repulsive interaction between adsorbed oxygen and (gas-phase) ethylene into an attractive one, thus making possible the epoxidation reaction. The presence of subsurface oxygen diminishes an important four-electron destabilizing interaction (Pauli repulsion) between the occupied ethylene {pi} orbital and a surface oxygen lone-pair orbital by shifting the band of ethylene {pi}-oxygen lone-pair antibonding orbitals largely above the Fermi level. As for total combustion of ethylene, we do not find any C-H bond activation for several different geometries in which ethylene approaches the adsorbed oxygen atom.

• OSTI ID: 6985639
• Journal Information: Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 93:17; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKENES
CALCULATION METHODS
CATALYSTS
DATA ANALYSIS
ELEMENTS
EPOXIDES
ETHYLENE
HYDROCARBONS
MATHEMATICAL MODELS
METALS
NONMETALS
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXYGEN
SILVER
TRANSITION ELEMENTS