Highly Efficient and Stable Ni–W Nanoalloy Catalyst for Selective Hydrogenation of Nitriles to Secondary Amines

Alloying with other metals is an effective strategy for enhancing the catalytic performance of intrinsically low-activity, non-precious metals. Liquid-phase reduction is a powerful method for synthesizing well-defined metal alloy nanoparticles with narrow size distributions and controlled structures; however, combining non-precious metals with early-transition metals remains largely unexplored due to their significantly different chemical properties. Herein, we report the development of a well-defined Ni–W nanoalloy (nano-NiW) by using a liquid-phase reduction method and its application as a heterogeneous catalyst for the hydrogenation of nitriles to secondary amines. The nano-NiW catalyst exhibited higher activity compared with monometallic Ni and conventionally impregnated Ni–W catalysts, enabling the selective nitrile hydrogenation to secondary amines even at 0.1 MPa H 2 . The catalyst also showed a broad substrate scope and could be recycled without loss of activity. Comprehensive structural and kinetic analyses revealed that incorporation of W into nano-NiW facilitates Schiff base reduction, a key step in the catalytic cycle. Overall, this study substantially advances the performance of Ni-based catalysts and offers a promising strategy for more efficient and economical organic synthesis.