Nitrogen-doped carbon materials featuring atomically dispersed metal cations (M-N-C) are an emerging family of materials with potential applications for electrocatalysis. The electrocatalytic activity of M-N-C materials toward four-electron oxygen reduction reaction (ORR) to H₂O is a mainstream line of research for replacing platinum-group-metal-based catalysts at the cathode of fuel cells. However, fundamental and practical aspects of their electrocatalytic activity toward two-electron ORR to H₂O₂, a future green "dream" process for chemical industry, remain poorly understood. Here we combined computational and experimental efforts to uncover the trends in electrochemical H₂O₂ production over a series of M-N-C materials (M = Mn, Fe, Co, Ni, and Cu) exclusively comprising atomically dispersed M-N_x sites from molecular first-principles to bench-scale electrolyzers operating at industrial current density. We investigated the effect of the nature of a 3d metal within a series of M-N-C catalysts on the electrocatalytic activity/selectivity for ORR (H₂O₂ and H₂O products) and H₂O₂ reduction reaction (H₂O₂RR). Co-N-C catalyst was uncovered with outstanding H₂O₂ productivity considering its high ORR activity, highest H₂O₂ selectivity, and lowest H₂O₂RR activity. The activity-selectivity trend over M-N-C materials was further analyzed by density functional theory, providing molecular-scale understandings of experimental volcano trends for four- and two-electron ORR. The predicted binding energy of HO* intermediate over Co-N-C catalyst is located near the top of the volcano accounting for favorable two-electron ORR. The industrial H₂O₂ productivity over Co-N-C catalyst was demonstrated in a microflow cell, exhibiting an unprecedented production rate of more than 4 mol peroxide g_catalyst^-1 h^-1 at a current density of 50 mA cm^-2.

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