LAUSR

Abstract The mechanism of CO oxidation on two-dimensional porphyrin sheet (TDPS)-supported single atom manganese was studied using density functional theory with dispersion (DFT-D). The molecular dynamics (MD) simulation based on the first principles has been used for confirming Mn–TDPS stability. The energetic calculations indicated that CO and O2 were favorable to co-adsorb at the active center. Eley–Rideal, Langmuir–Hinshelwood (LH), and tri-molecular Eley–Rideal (TER) mechanisms were used to investigate the reaction pathways of CO oxidation on the Mn–TDPS. Results indicated that the LH and TER reaction mechanisms were feasible due to the small energy barrier of the rate-determining step. Moreover, the oxidation states of the active center of Mn–TDPS affected the reaction barrier and reaction heat, which was unfavorable for CO oxidation in Mn–TDPS. These results findings suggested that Mn–TDPS could be a high activity catalyst for CO oxidation.