A Comprehensive Study on the Reductive Amination of 5-Hydroxymethylfurfural into 2,5-Bisaminomethylfuran over Raney Ni Through DFT Calculations
A Comprehensive Study on the Reductive Amination of 5-Hydroxymethylfurfural into 2,5-Bisaminomethylfuran over Raney Ni Through DFT Calculations
复制标题
通过DFT计算综合研究5-羟甲基糠醛在雷尼镍上还原胺化生成2,5-双氨基甲基呋喃
DOI：
10.1002/cctc.201900304
复制
发表时间：
2019-06-06
期刊：
影响因子：
4.5
通讯作者：
Li, Xiaonian
中科院分区：
文献类型：
--
作者：
Zhou, Kuo;Liu, Haiyan;Li, Xiaonian
在不同的金属催化剂上进行了糠醇、糠醛和5-羟甲基糠醛的还原胺化反应。在Raney Ni催化剂上，在无氢存在和有氢存在下，糠醇的最高糠胺收率分别为81.8%和94.0%。以糠醛为底物，在较温和的条件下，雷尼镍催化剂上糠胺的产率可达100%。尽管5-HMF在所有使用的催化剂上完全转化，但在Raney Ni上在160 ° C下在12小时内获得2，5-双氨基甲基呋喃的最高产率（60.7%）。对NH3和H2-在不同金属表面吸附行为的DFT计算表明，NH3和H2-在Ni表面的吸附能差小于其它金属表面的吸附能差，表明NH3在Ni表面占据了较少的金属活性位，为脱氢/加氢反应留下了较多的活性位，最终促进了还原胺化反应.
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 H-2, 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 degrees C in 12 h. The DFT calculations on the adsorption behavior of NH3 and H-2 on different metal surfaces showed that the difference of the adsorption energy between NH3 and H-2 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.