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 dxz and dz2 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.