High‐Efficiency Electrosynthesis of Hydrogen Peroxide from Oxygen Reduction Enabled by a Tungsten Single Atom Catalyst with Unique Terdentate N1O2 Coordination

Abstract Single‐atom catalysts (SACs) have shown great potential in the electrochemical oxygen reduction reaction (ORR) toward hydrogen peroxide (H 2 O 2 ) production. However, current studies are mainly focused on 3d transition‐metal SACs, and very little attention has been paid to 5d SACs. Here, a new kind of W SAC anchored on a porous O, N‐doped carbon nanosheet (W 1 /NO‐C) is designed and prepared via a simple coordination polymer‐pyrolysis method. A unique local structure of W SAC, terdentate W 1 N 1 O 2 with the coordination of two O atoms and one N atom, is identified by the combination of aberration‐corrected scanning transmission electron microscopy, X‐ray photoelectron spectroscopy and X‐ray absorption fine structure spectroscopy. Remarkably, the as‐prepared W 1 /NO‐C catalyzes the ORR via a 2e – pathway with high onset potential, high H 2 O 2 selectivity in the wide potential range, and excellent operation durability in 0.1 m KOH solution, superior to most of state‐of‐the‐art H 2 O 2 electrocatalysts ever reported. Theoretical calculations reveal that the C atoms adjacent to O in the W 1 N 1 O 2 ‐C moiety are the most active sites for the 2e – ORR to H 2 O 2 with the optimal binding energy of the HOO* intermediate. This work opens up a new opportunity for the development of high‐performance W‐based catalysts for electrochemical H 2 O 2 production.