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

Abstract

AbstractSingle‐atom catalysts (SACs) have shown great potential in the electrochemical oxygen reduction reaction (ORR) toward hydrogen peroxide (H2O2) 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 (W1/NO‐C) is designed and prepared via a simple coordination polymer‐pyrolysis method. A unique local structure of W SAC, terdentate W1N1O2 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 W1/NO‐C catalyzes the ORR via a 2e– pathway with high onset potential, high H2O2 selectivity in the wide potential range, and excellent operation durability in 0.1 m KOH solution, superior to most of state‐of‐the‐art H2O2 electrocatalysts ever reported. Theoretical calculations reveal that the C atoms adjacent to O in the W1N1O2‐C moiety are the most active sites for the 2e– ORR to H2O2 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 H2O2 production.