Modulation of Topological Order in Structural Unit of Nitrides for Enhanced Electrosynthesis of Nitrile

Abstract The electrochemical oxidation of amines has emerged as a promising alternative to traditional energy‐intensive industrial processes for the green synthesis of nitriles, and the rational design of efficient electrocatalysts is crucial due to the sluggish reaction kinetics. Herein, it is reported that modulating the topological order within the same structural unit can boost catalytic activity for the electrooxidation of benzylamine to benzonitrile (BOR). Using nickel nitride as a model, Cu atoms are introduced into the pristine N─Ni structural framework, inducing a change in the topological order of the structural units and resulting in the formation of Ni 3 CuN with an antiperovskite structure. As a result, the antiperovskite Ni 3 CuN exhibits a 2‐fold enhancement of BOR activity compared to Ni 3 N, despite the fact that the N─Ni coordination polyhedra of both are almost identical. Theoretical calculations demonstrate that the modulation strategy of the topological order of the same structural units successfully weakens the Ni─N bonding interactions, induces the downward shift of the d‐band centers, and optimizes the desorption of the reaction products, which ultimately contributes to the more superior electrocatalytic activity of Ni 3 CuN. This work provides a new perspective on developing advanced electrocatalysts through the structural topological order modulation.