Ambient‐Temperature Reductive Amination of 5‐Hydroxymethylfurfural Over Al2O3‐Supported Carbon‐Doped Nickel Catalyst

Abstract An efficient catalytic system for the conversion of 5‐hydroxymethylfurfural (HMF) into N‐containing compounds over low‐cost non‐noble‐metal catalysts is preferable, but it is challenging to reach high conversion and selectivity under mild conditions. Herein, an Al 2 O 3 ‐supported carbon‐doped Ni catalyst was obtained via the direct pyrolysis‐reduction of a mixture of Ni 3 (BTC) 2 ⋅ 12H 2 O and Al 2 O 3 , generating stable Ni 0 species due to the presence of carbon residue. A high yield of 96 % was observed in the reductive amination of HMF into 5‐hydroxymethyl furfurylamine (HMFA) with ammonia and hydrogen at ambient temperature. The catalyst was recyclable and could be applied to the ambient‐temperature synthesis of HMF‐based secondary/tertiary amines and other biomass‐derived amines from the carbonyl compounds. The significant performance was attributable to the synergistic effect of Ni 0 species and acidic property of the support Al 2 O 3 , which promoted the selective ammonolysis of the imine intermediate while inhibiting the potential side reaction of over‐hydrogenation.