| Abstract
| - The heterogeneously catalyzed epoxidation of alkenes is experimentally challenging, theoretically interesting, and technologically important. Although large-scale ethylene epoxidation is universally carried out with Ag catalysts, recent laboratory studies on single crystal surfaces show that Cu is intrinsically much more selective than Ag in the epoxidation of a variety of terminal alkenes. The reasons for this striking difference between Ag and Cu have been investigated by means of density functional theory. It is found that the fundamental cause is the inversion in the ordering of activation barriers for the competing pathways to epoxide formation versus acetaldehyde formation (the latter being the first step on the route to combustion). On Cu, epoxide formation is less activated than aldehyde formation; the opposite is true on Ag. This behavior is associated with a late transition state to epoxidation on Cu (i.e., product-like) compared to an early (reactant-like) transition state to epoxidation on Ag.
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