PNNL

Abstract

Correlated molecular orbital theory at the coupled cluster CCSD(T) level with density functional theory geometries is used to study ethanol dehydration, dehydrogenation, and condensation reactions on an the Al8O12 cluster which is a model for ?-Al2O3. The Al in the active site on the cluster is a strong Lewis acid. The reactions begin with formation of a very stable Lewis acid–base ethanol–cluster adduct. Dehydration proceeds by ß-H transfer to a bicoordinate oxygen leading to the direct formation of ethylene and two OH groups following an E2 mechanism. Dehydrogenation proceeds directly by a-H transfer to the active metal center and a proton transfer to a bicoordinate bridge O to form acetaldehyde plus a metal hydride and a hydroxyl, again an E2 mechanism. After addition of a second ethanol, diethyl ether is generated by an a-C transfer from the first to the second ethanol, an acid-driven SN2 mechanism. Condensation and dehydration with two alcohols have comparable energy barriers. The addition of a second ethanol or a water molecule raises the energy barriers. Condensation and dehydration are predicted to be more likely than dehydrogenation. The computational results for the mechanism and the energetics agree well with the available experimental data.