Biphasic Transition Metal Nitride Electrode Promotes Nucleophile Oxidation Reaction for Practicable Hybrid Water Electrocatalysis

Abstract Glycerol electrooxidation (GOR), as a typical nucleophile oxidation reaction, is deemed as a promising alternative anodic route to assist cathodic hydrogen evolution reaction. However, the investigations of high‐performance catalysts and industrial‐scale application of GOR remain a grand challenge. Herein, biphasic Ni3N/Co3N heterostructure nanowires (denoted as Ni3N/Co3N‐NWs) are proposed as an efficient bifunctional catalyst, which realizes a high Faradaic efficiency of 94.6% toward formate production. Importantly, the flow electrolyzer achieves an industry‐level current density of 1 A cm−2 at 2.01 V with impressive stability for steady running over 200 h, realizing lower electricity expense of 4.82 kWh m−3H2 and energy saving efficiency of 9.7%, as well as outstanding co‐production rates of 11 and 21.4 mmol cm−2 h−1 toward formate and H2, respectively. Theoretical calculations reveal that the efficient electron transfer on Ni3N/Co3N heterointerfaces simultaneously optimizes nucleophile reaction tendency and glycerol dehydrogenation kinetics, thus contributing to excellent GOR performance.