Carbon‐supported NiII single‐atom catalysts with a tetradentate Ni‐N2O2 coordination formed by a Schiff base ligand‐mediated pyrolysis strategy are presented. A NiII complex of the Schiff base ligand (R,R)‐(−)‐N,N′‐bis(3,5‐di‐tert‐butylsalicylidene)‐1,2‐cyclohexanediamine was adsorbed onto a carbon black support, followed by pyrolysis of the modified carbon material at 300 °C in Ar. The Ni‐N2O2/C catalyst showed excellent performance for the electrocatalytic reduction of O2 to H2O2 through a two‐electron transfer process in alkaline conditions, with a H2O2 selectivity of 96 %. At a current density of 70 mA cm−2, a H2O2 production rate of 5.9 mol gcat.−1 h−1 was achieved using a three‐phase flow cell, with good catalyst stability maintained over 8 h of testing. The Ni‐N2O2/C catalyst could electrocatalytically reduce O2 in air to H2O2 at a high current density, still affording a high H2O2 selectivity (>90 %). A precise Ni‐N2O2 coordination was key to the performance.

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