Dissociative adsorption of CO2 on flat, stepped, and kinked Cu surfaces.

We studied the dissociative adsorption of CO₂ to CO + O on the Cu(111), Cu(221), Cu(211), and Cu(11 5 9) surfaces by using state-of-the-art density functional theory (DFT) within a generalized gradient approximation (GGA) and van der Waals density functional (vdW-DF) calculations. The activation energy for CO2 dissociation on the flat Cu(111) surface is 1.33 eV. The activation energies on stepped and kinked surfaces are 1.06 eV, 0.67 eV, and 1.02 eV for the Cu(221), Cu(211), and Cu(11 5 9) surfaces, respectively. Even though the activation energy is 0.66 eV lower on the stepped Cu(211) surface than on the flat Cu(111) surface, we conclude that CO₂ does not dissociate on "ideal" flat, stepped, or kinked Cu surfaces at low temperature. We attribute the discrepancy between our theoretical results and experimentally observed CO₂ dissociation on stepped Cu surfaces below 150 K to other factors such as effects of Cu adatoms, gas phase or condensed CO₂ molecules, or interaction with other gas phase molecules. [ABSTRACT FROM AUTHOR]