A Comprehensive Study on the Reductive Amination of 5‐Hydroxymethylfurfural into 2,5‐Bisaminomethylfuran over Raney Ni Through DFT Calculations

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 furfur...

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Bibliographic Details
Published in:ChemCatChem 2019-06, Vol.11 (11), p.2649-2656
Main Authors: Zhou, Kuo, Liu, Haiyan, Shu, Huimin, Xiao, Shuwen, Guo, Dechao, Liu, Yingxin, Wei, Zuojun, Li, Xiaonian
Format: Article
Language:English
Subjects:
5-Hydroxymethylfurfural
Adsorption
Alcohol
Ammonia
Biomass
Catalysis
Catalysts
Dehydrogenation
Furfural
Furfuryl alcohol
Hydroxymethylfurfural
Mathematical analysis
Metal surfaces
Nickel
Raney Ni
Reductive amination
Substrates
Surface chemistry
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Summary: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. Raney to the rescue! High value‐added 2,5‐bisaminomethylfuran was one‐pot synthesized from 5‐HMF over Raney Ni with a yield of 60.7 %. DFT calculations were conducted to support our speculation that Ni can harmonize NH3 and H2 on its surface most suitably for the reductive amination reactions.
ISSN:1867-3880
1867-3899
DOI:10.1002/cctc.201900304