Amine Coordinated Electron‐Rich Palladium Nanoparticles for Electrochemical Hydrogenation of Benzaldehyde

Abstract Electrocatalytic hydrogenation (ECH) is a burgeoning strategy for the sustainable utilization of hydrogen. However, how to effectively suppress the competitive hydrogen evolution reaction (HER) is a big challenge to ECH catalysis. In this study, amine (NH 2 R)‐coordinated Pd nanoparticles loaded on carbon felt (Pd@CF) as a catalyst is successfully synthesized by a one‐step solvothermal reduction method using oleylamine as the reducing agent. An exceptional ECH reactivity on benzaldehyde is achieved on the optimal Pd@CF catalyst in terms of a high conversion (89.7%) and selectivity toward benzyl alcohol (89.8%) at −0.4 V in 60 min. Notably, the Faradaic efficiency for producing benzyl alcohol is up to 90.2%, much higher than that catalyzed by Pd@CF‐without N‐group (41.1%) and thecommercial Pd/C (20.9%). The excellent ECH performance of Pd@CF can be attributed to the enriched electrons on Pd surface resulted from the introduction of NH 2 R groups, which strengthens both the adsorption of benzaldehyde and the adsorbed hydrogen (H ads ) on Pd, preventing the combination of H ads to form H 2 , that is, inhibiting the HER. This study gives a new insight into design principles of highly efficient electrocatalysts for the hydrogenation of unsaturated aldehydes molecules.