First Principles Study on the CO Oxidation on Mn-Embedded Divacancy Graphene

The CO oxidation mechanism on graphene with divacancy (DG) embedded with transition metal from Sc to Zn has been studied by using first principles calculations. The results indicate that O(2) molecule is preferentially adsorbed on Sc, Ti, V, Cr, Mn, and Fe-DG, which can avoid the CO poisoning problem that many catalysts facing and is beneficial to the CO oxidation progress. Further study indicates that Mn-DG shows the best catalytic properties for CO oxidation with consideration of both Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) oxidation mechanisms. Along the ER mechanism, the reaction energy barrier for the first step (CO (free) + O(2) (pre-adsorbed) → OOCO) is 0.96 eV. Along the LH mechanism, the energy barrier for the rate limiting step (CO (adsorbed) + O(2) (adsorbed) → OOCO) is only 0.41 eV, indicating that the CO oxidation on Mn-DG will occur along LH mechanism. The Hirshfeld charge distributions of O(2) and CO molecules is tuned by the embedded Mn atom, and the charge transfer from the embedded Mn atom to the adsorbed molecules plays an important role for the CO oxidation. The result shows that the Mn-embedded divacancy graphene is a noble-metal free and efficient catalyst for CO oxidation at low temperature.