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Efficient strategy for fructose conversion to 2,5-furandicarboxylic acid, 2,5-dicarbonylfuran or 5-formyl-2-furancarboxylic acid over dual single-atomic Fe/Co catalyst

Journal 2025 · IF 13.2 · 发表于 2025 年 10 月 12 日
作者: Maolin Li,Quanxi Lu,Zhichao Dong,Sijie Liu,Rong Tan
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摘要

5-Hydroxymethylfurfural (HMF), which is obtained from fructose dehydration, can be oxidized to valuable biomass-based platform chemicals, such as 2,5-furandicarboxylic acid (FDCA), 2,5-dicarbonylfuran (DFF) and 5-formyl-2-furancarboxylic acid (FFCA). However, the complex reactions of dehydration and oxidations make it is still challenging to obtain these chemicals from fructose. Herein, a dual single-atomic Fe/Co composed of isolated FeN 6 and CoN 5 sites supported on N-doped carbon (Fe/Co-NC) was constructed to efficient conversion of fructose to FDCA, DFF or FFCA through a two-step strategy. Owing to the Lewis acid sites in Fe/Co-NC, fructose can efficiently convert to HMF with an isolated yield of 91.70 % at 145 °C in dimethyl sulfoxide (DMSO). Furthermore, synergistic effect between Fe and Co atoms, which results in charge redistribution, can also promote the adsorption and activation of HMF and O 2 for efficient oxidation. Attributing to the various ability of Fe/Co-NC to activate O 2 in different solvents, superoxide radicals (·O 2 − ) generated in MeCN result in 97.70 % yield of DFF, while peroxyl radicals (·OOH) generated in water lead to 97.29 % yield of FDCA. Adding DMSO in aqueous system seriously hinders the reaction rate (rate constant from 0.0022 to 0.0008 min −1 ) due to solvation of HMF by DMSO, resulting in high yield of FFCA (81.56 %) at 4 h. Therefore, controllable conversion of FDCA, DFF or FFCA from fructose is achieved over Fe/Co-NC, and the readily recovered method and good stability of the catalyst also indicate the prospect for continuous production of the above chemicals from fructose in the future.

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