Termolecular Eley–Rideal pathway for efficient CO oxidation on phosphorene‐supported single‐atom cobalt catalyst

Abstract

AbstractDensity functional theory calculations are conducted to examine the oxidation of CO on a single Co atom anchored on a two‐dimensional phosphorene monolayer (Co@Pn). The stability of the Co adatom on the Pn monolayer was revealed by ab initio molecular dynamics simulations. Three plausible pathways for CO oxidation over Co@Pn were explored: Langmuir–Hinshelwood (LH), Eley–Rideal (ER), and the recently proposed termolecular Eley–Rideal (TER) mechanisms. The TER pathway has a relatively lower energy barrier for the rate‐determining step (0.55) than those of the LH (0.81) and ER (0.70 eV) pathways. The efficiency of TER pathway can be interpreted by CO‐promoted O2 activation via the effective formation of a five‐membered ring composed of two CO and one O2 molecules. The results open a new avenue for developing phosphorene‐supported non‐noble transition metal single‐atom catalysts for various catalytic applications.