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 O₂ and CO₂ 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_z² orbitals, pivotal for stabilizing the π* orbitals of O₂. 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.