Catalytic electroreduction of benzonitrile offers a promising sustainable alternative to thermocatalytic approaches for benzylamine synthesis under mild conditions. Inspired by a decoupling strategy, herein, we rationally constructed dual-active sites of Cu+ and Cu0 within Cu2O/Cu nanowire array (Cu2O/Cu-NA) electrocatalysts for water and benzonitrile activation, respectively. This design enabled exceptional catalytic performance for benzonitrile-to-benzylamine electroreduction. Precise control of the electroreduction potentials of CuO nanowire array for the synthesis of Cu2O/Cu-NA allowed the modulation of Cu+/Cu0 ratios. A volcano-shaped correlation was observed between the electrocatalytic activity of Cu2O/Cu-NA and Cu+/Cu0 ratios. Experimentally, the Cu2O/Cu-NA with a Cu+/Cu0 ratio of 0.98 delivered the optimal catalytic performance with a benzonitrile conversion of 99.8%, a benzylamine selectivity of 98.7% and a Faradaic efficiency of 98.8% at -0.37 V vs. RHE. Comprehensive mechanistic investigations demonstrate the distinct roles of Cu+ in generating *H through water activation and Cu0 in activating/reducing benzonitrile. The intimate Cu2O/Cu interface facilitates kinetic matching between the *H generation and nitrile reduction, leading to selective benzonitrile-to-benzylamine transformation and suppressing side reactions and the competing hydrogen evolution reaction.
Jiang et al. (2026) studied this question.