Selective Electrochemical Amine‐to‐Nitrile Conversion on Nickel−Cobalt Hydrogen Phosphate Nanowires Coupled with Hydrogen Generation

Abstract Developing highly active electrocatalysts for the benzylamine oxidation reaction (BOR) is very imperative for organic compounds upgrading. Meanwhile, clarifying the underlying BOR mechanism is of remarkable significance but still confronts challenges. Herein, bimetallic nickel‐cobalt hydrogen phosphate nanowires (NiCo‐HPNWs) are put forward as a high‐performance anodic catalyst for selective BOR. Furthermore, NiCo‐HPNWs is used as a proof‐of‐concept model to understand the synergistic effects between Ni and Co atoms during the BOR process. It is found that NiCo‐HPNWs catalyst shows excellent electrocatalytic BOR performance, with a small onset potential of 0.265 V versus. Ag/AgCl and a high faradic efficiency (FE) of 93.0% for benzonitrile (BN) production at 0.40 V versus. Ag/AgCl. Also, the FEs for BN production can reach ≈80% at voltages from 1.50 to 1.65 V by coupling the BOR with the hydrogen evolution reaction in a two‐electrode electrolyzer. Potential‐dependent in situ Raman spectroscopy sheds light on the direct electro‐oxidation mechanism of benzylamine (BA) over the NiCo‐HPNWs catalyst. In combination with X‐ray photoelectron spectroscopy and density functional theory calculations, the charge transfer behavior between Ni and Co atoms is revealed, which endows NiCo‐HPNWs with a favorable charge distribution to promote BA adsorption and BN desorption on the catalyst surface, thereby leading to expedited reaction kinetics and enhanced electrochemical BOR activity.