Reductive amination of furfuryl alcohol, furfural and 5‐hydroxymethylfurfural (5‐HMF) were carried out on various metal catalysts. Over Raney Ni catalyst, we obtained the highest furfurylamine yields of 81.8 % and 94.0 % from furfuryl alcohol in absence and presence of H2, respectively. While furfural was used as the substrate, 100 % yield of furfurylamine could be achieved over Raney Ni under rather moderate conditions. Although 5‐HMF was completely converted over all catalysts used, the highest yield of 2,5‐bisaminomethylfuran (60.7 %) was obtained over Raney Ni at 160 °C in 12 h. The DFT calculations on the adsorption behavior of NH3 and H2 on different metal surfaces showed that the difference of the adsorption energy between NH3 and H2 on Ni is lower than those of other metals, indicating that less metal active sites on Ni surface is occupied by NH3, which leaves more active sites for dehydrogenation/hydrogenation reactions and in the end promotes the reductive amination reactions.
Switchable reductive amination of furfuryl alcohol to tetrahydrofurfurylamine and furfurylamine was realized by adding/not adding H2 over a RANEY® Ni catalyst.
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