Boosting Hydrogen Production by Anodic Oxidation of Primary Amines over a NiSe Nanorod Electrode

Abstract For electrocatalytic water splitting, the sluggish anodic oxygen evolution reaction (OER) restricts the cathodic hydrogen evolution reaction (HER). Therefore, developing an alternative anodic reaction with accelerating kinetics to produce value‐added chemicals, especially coupled with HER, is of great importance. Now, a thermodynamically more favorable primary amine (−CH 2 −NH 2 ) electrooxidation catalyzed by NiSe nanorod arrays in water is reported to replace OER for enhancing HER. The increased H 2 production can be obtained at cathode; meanwhile, a variety of aromatic and aliphatic primary amines are selectively electrooxidized to nitriles with good yields at the anode. Mechanistic investigations suggest that Ni II /Ni III may serve as the redox active species for the primary amines transformation. Hydrophobic nitrile products can readily escape from aqueous electrolyte/electrode interface, avoiding the deactivation of the catalyst and thus contributing to continuous gram‐scale synthesis.