Intrinsic Activity of Metal Centers in Metal-Nitrogen-Carbon Single-Atom Catalysts for Hydrogen Peroxide Synthesis

Metal-nitrogen-carbon (M-N-C) single-atom catalysts (SACs) show high catalytic activity for many important chemical reactions. However, an understanding of their intrinsic catalytic activity remains ambiguous because of the lack of well-defined atomic structure control in current M-N-C SACs. Here, we use covalent organic framework SACs with an identical metal coordination environment as model catalysts to elucidate the intrinsic catalytic activity of various metal centers in M-N-C SACs. A pH-universal activity trend is discovered among six 3d transition metals for hydrogen peroxide (H₂O₂) synthesis, with Co having the highest catalytic activity. Using density functional calculations to access a total of 18 metal species, we demonstrate that the difference in the binding energy of O₂* and HOOH* intermediates (E_O - E_HOOH*) on single metal centers is a reliable thermodynamic descriptor to predict the catalytic activity of the metal centers. The predicted high activity of Ir centers from the descriptor is further validated experimentally. This work suggests a class of structurally defined model catalysts and clear mechanistic principles for metal centers of M-N-C SACs in H₂O₂ synthesis, which may be further extendable to other reactions.