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 (H 2 O 2 ) 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 O 2 * and HOOH* intermediates ( E O 2 * – 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 H 2 O 2 synthesis, which may be further extendable to other reactions.