Brønsted acid–metal synergy in Ni/HZSM-5 for reductive amination of biomass-derived furfural to furfurylamine

The sustainable synthesis of primary amines from renewable biomass is a key goal of green chemistry. Reductive amination of furfural (FAL), a representative biomass platform molecule, provides a direct route to furfurylamine (FAM), yet noble-metal catalysts remain dominant in this field, limiting large-scale application due to high cost and scarcity. Herein, we report non-noble Ni/HZSM-5 catalysts with tunable SiO 2 /Al 2 O 3 ratios that achieve up to 99% yield of FAM with a high generation rate (10.8 mmol FAM mmol Ni −1  h −1 ) under mild conditions (90 °C, 1 MPa H 2 , 0.8 MPa NH 3 ). Mechanistic studies reveal that the synergistic interface between metallic Ni and Brønsted acid sites facilitates hydrogen activation and spillover, enhances imine adsorption, and stabilizes gem- diamine and is beneficial for its ammonolysis. The catalyst also demonstrates excellent recyclability and broad substrate scope, affording >90% yields of primary amines for the reductive amination of the various aldehydes and ketones. This work provides mechanistic insights into Brønsted acid–metal synergy and establishes a sustainable, cost-effective strategy for the green synthesis of primary amines.