Electrochemical Potential-Driven Shift of Frontier Orbitals in M-N-C Single-Atom Catalysts Leading to Inverted Adsorption Energies.

Electronic structure is essential to understanding the catalytic mechanism of metal single-atom catalysts (SACs), especially under electrochemical conditions. This study delves into the nuanced modulation of "frontier orbitals" in SACs on nitrogen-doped graphene (N-C) substrates by electrochemical potentials. We observe shifts in Fermi level and changes of d-orbital occupation with alterations in electrochemical potentials, emphasizing a synergy between the discretized atomic orbitals of metals and the continuous bands of the N-C based environment. Using O 2 and CO 2 as model adsorbates, we highlight the direct consequences of these shifts on adsorption energies, unveiling an intriguing inversion of adsorption energies on Co/N-C SAC under negative electrochemical potentials. Such insights are attributed to the role of the d xz and d z 2 orbitals, pivotal for stabilizing the π* orbitals of O 2 . Through this exploration, our work offers insights on the interplay between electronic structures and adsorption behaviors in SACs, paving the way for enhanced catalyst design strategies in electrochemical processes.