Effect of surface and oxygen coverage on ethylene expoxidation

Ethylene epoxidation was studied as a function of oxygen coverage; for three different surfaces (111), (100) and (110) of three different IB metals using periodical DFT calculations. Oxygen coverage dependence was tested for 11, 25 and 33 % surface oxygen on Ag(111) surface. Calculations showed that increasing oxygen amount increased the exothermicity of the reaction while lowering the activation barriers. At studied oxygen ratios ethylene oxide and acetaldehyde formations proceed through OMC intermediate. In agreement with earlier studies, predicted selectivity is independent of surface structure. Generally the activation barriers for aldehyde formation are lower than those for epoxide formation on the studied surfaces. On copper surfaces the high stability of the precursor intermediates caused high activation barriers for the product formations. Also, epoxide formation is endothermic with respect to pre-oxygenated copper surfaces. On the other hand gold surfaces showed the smallest activation barriers for the product formations. Ag surfaces did not show conclusive differences for the activation barriers for epoxide versus aldehyde formation, which is in agreement with the *50 % EO selectivity of the un-promoted metallic silver.