One-Pot Amination of 5-Hydroxymethylfurfural to 2,5-Bis(aminomethyl)furan over NiZnAl Catalysts

This study developed a highly efficient one-step catalytic reductive amination method, achieving the highly selective conversion of 5-hydroxymethylfurfural (HMF) to 2,5-bis(aminomethyl)furan (BAMF). A series of NiZnAl catalysts were prepared via the coprecipitation method and demonstrated excellent catalytic performance in HMF conversion. The Ni4Zn4Al8Ox catalyst achieved up to 100% substrate conversion with 83.71% BAMF selectivity. Their structure–activity relationship was elucidated through a comprehensive characterization using XRD, H2-TPR, NH3-TPD, XPS, and TEM techniques. The study reveals that the unique synergistic interactions between the metal and acidic sites on the ZnAl2O4 spinel structure is crucial for catalytic performance: on the one hand, Zn introduction forms the spinel structure and promotes electron enrichment at Ni active sites, significantly enhancing the activation capability of HMF hydroxyl groups; on the other hand, the moderately acidic sites in the catalyst form “metal-acid” dual-functional synergistic centers with the metal sites, simultaneously promoting substrate activation and effectively regulating the transformation pathways of reaction intermediates. This precise matching between the metal active sites and acidic sites enables the efficient sequential progression of all steps in the reaction, offering a novel and more selective solution for the efficient reductive amination of HMF.