Structural Evolution and Underlying Mechanism of Single-Atom Centers on Mo₂C(100) Support during Oxygen Reduction...

The single-metal atoms coordinating with the surface atoms of the support constitute the active centers of as-prepared single-atom catalysts (SACs). However, under hash electrochemical conditions, (1) supports' surfaces may experience structural change, which turn to be distinct from those at ambient conditions; (2) during catalysis, the dynamic responses of a single atom to the attack of reaction intermediates likely change the coordination environment of a single atom. These factors could alter the performance of SACs. Herein, we investigate these issues using Mo₂C(100)-supported single transition-metal (TM) atoms as model SACs toward catalyzing the oxygen reduction reaction (ORR). It is found that the Mo₂C(100) surface is oxidized under ORR turnover conditions, resulting in significantly weakened bonding between single TM atoms and the Mo₂C(100) surface (TM@Mo₂C(100)_O* term for SAC). While the intermediate in 2 e^- ORR does not change the local structures of the active centers in these SACs, the O* intermediate emerging in 4 e^- ORR can damage Rh@ and Cu@Mo₂C(100)_O*. Furthermore, on the basis of these findings, we propose Pt@Mo₂C(100)_O* as a qualified ORR catalyst, which exhibits extraordinary 4 e^- ORR activity with an overpotential of only 0.33 V, surpassing the state-of-the-art Pt(111), and thus being identified as a promising alternative to the commercial Pt/C catalyst.