Partial oxidation of methanol on Cu(110): Energetics and kinetics

The reaction pathway of the partial oxidation of methanol to formaldehyde on clean and oxygen-precovered Cu(110) has been studied by density functional theory calculations within the generalized gradient approximation. Dosing the Cu surfaces with oxygen promotes the methanol oxidation by stabilizing the methoxy intermediate on Cu and inducing the removal of surface hydrogen via water desorption. Using the information from the total-energy calculations in kinetic Monte Carlo simulations, the temperature programmed desorption of methanol was addressed thus yielding information on the microscopic details of the oxidation kinetics and the accuracy of the calculated barriers. (c) 2006 Elsevier B.V. All rights reserved.