Promoting Heterogeneous Nickel Catalysis with Surface-Atomically Dispersed Tungstate Species

Highly selective reductive amination using nonprecious metal catalysts is an important approach for the synthesis of specialty functional amines. However, due to the inherent electronic structure of nonprecious metals, their practical applications often face challenges such as low activity, poor selectivity, and insufficient stability (e.g., susceptibility to oxidation). In this work, by leveraging the strong interaction between nonprecious metals and oxygen atoms, we developed effective strategies, including in situ hydrolysis and thermal decomposition, to achieve the deposition of mononuclear [WO 4 ] 2– species on the Ni surface. Systematic studies reveal that the unique acid–base and redox properties of the mononuclear [WO 4 ] 2– species effectively promote proton and electron transfer, thereby significantly enhancing the catalytic activity and selectivity in the reductive amination of aldehydes and ketones to produce functional amines. This work successfully creates earth-abundant catalysts that outperform noble metal catalysts under identical reaction conditions, exhibiting catalytic performance several orders of magnitude higher than previously reported catalysts. Moreover, these catalysts demonstrate exceptional applicability in the production of a wide range of pharmaceuticals and industrial fine chemicals, holding great promise for broad industrial adoption.