Control of ethylene epoxidation selectivity by surface oxametallacycles. Academic Article

abstract

• Surface science experiments, DFT calculations, and kinetic isotope effect data are utilized to understand the elementary steps that govern the selectivity of silver catalysts for the partial oxidation of ethylene to produce ethylene oxide. It is proposed that selective and unselective pathways proceed via a common intermediate, the surface oxametallacycle. The structures of the transition states leading from this intermediate to selective and unselective products are calculated. From the calculated Gibbs free energies of activation for competing pathways, it is possible to predict selectivity to ethylene oxide as well as the magnitude of the kinetic isotope effect. The proposed mechanism is qualitatively and quantitatively in accord with experimental results.

authors

• Barteau, Mark

published proceedings

• J Am Chem Soc

author list (cited authors)

• Linic, S., & Barteau, M. A.

citation count

• 174

complete list of authors

• Linic, Suljo||Barteau, Mark A

publication date

• April 2003

publisher

• American Chemical Society (ACS)  Publisher

published in

• Journal of the American Chemical Society  Journal

keywords

• 0306 Physical Chemistry (incl. Structural)

PubMed Central ID

• 12670209

Digital Object Identifier (DOI)

• 10.1021/ja029076g

start page

• 4034

end page

• 4035

volume

• 125

issue

• 14

URL

• http://dx.doi.org/10.1021/ja029076g