Highly Selective Hydrogenation of Benzonitrile to Benzylamine on Palladium–Nickel Heterogeneous Catalysts

ABSTRACT Benzylamine (BA), a vital chemical intermediate, is traditionally synthesized via the hydrogenation of benzonitrile (BN). However, this process often suffers from poor selectivity toward BA over monometallic Pd catalysts, leading to by‐products like toluene and dibenzylamine (DBA). Herein, we report a series of Pd–Ni bimetallic heterogeneous catalysts for the highly selective hydrogenation of BN to BA under mild conditions. The optimized Pd 3 Ni/TiO 2 catalyst exhibited exceptional performance at 50 °C and 0.2 MPa H 2 , achieving a BN conversion of 97.0% and a BA selectivity of 95.0%, significantly outperforming its monometallic Pd/TiO 2 counterpart. Comprehensive characterization revealed that alloying Pd with Ni modulates the electronic structure of Pd, enhancing the activation of BN while weakening the strong adsorption of the BA product and key intermediates. This differential adsorption tuning effectively suppresses over‐hydrogenation and coupling side reactions. Furthermore, the Pd 3 Ni/TiO 2 catalyst demonstrated excellent stability over 10 catalytic cycles. This work provides an effective strategy for designing efficient and selective hydrogenation catalysts through bimetallic synergy.