Exploiting Antisite Defects in FeWN₂ Nanosheets for Enol Electro‐oxidation Coupled with H₂ Evolution at a Large Current Density

Abstract Hydrogen production from biomass electro‐oxidation offers a promising alternative to water electrolysis by lowering the anodic oxidation barrier and producing valuable chemicals. However, current biomass electro‐oxidation systems have difficulties in achieving an industrial‐scale current density due to the difficulty in cleaving high‐energy C─H and O─H bonds. Here, we report a ternary layer nitride FeWN 2 electrocatalyst with abundant antisite defects (ASDs), which significantly improves its electrocatalytic performance for ascorbic acid (AA) oxidation. The catalyst works at a remarkable current density of 2.5 A cm −2 at 0.69 V (vs RHE) and achieves 4 A cm −2 at 1.12 V in a two‐electrode electrolyzer at 60 °C with 100% Faraday efficiency for H 2 production. Theoretical calculations reveal that W atoms near antipodal Fe sites replenish the electron density of Fe, maintaining moderate Fe‐DHA adsorption strength induced by ASDs that achieve superior catalytic efficiency for AA‐to‐DHA conversion This study provides new insight for developing high‐performance organic oxidation catalysts with ASDs.