Citation: Jiahan Xie, Junfang Nie, Haichao Liu. Aqueous-phase selective aerobic oxidation of 5-hydroxymethylfurfural on Ru/C in the presence of base[J]. Chinese Journal of Catalysis, ;2014, 35(6): 937-944. doi: 10.1016/S1872-2067(14)60136-4 shu

Aqueous-phase selective aerobic oxidation of 5-hydroxymethylfurfural on Ru/C in the presence of base

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Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Stable and Unstable Species, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

Corresponding author: Haichao Liu,
Received Date: 28 April 2014
Available Online: 30 April 2014
Fund Project: This work was supported by the National Basic Research Program of China (973 Program, 2011CB201400, 2011CB808700) (973 Program, 2011CB201400, 2011CB808700)the National Natural Science Foundation of China (21373019, 21173008). (21373019, 21173008)

The aerobic oxidation of 5-hydroxymethylfurfural (HMF) was performed on an activated carbon-supported ruthenium (Ru/C) catalyst in water. The presence of Mg-Al hydrotalcite (HT, Mg/Al molar ratio=3/1) as a base afforded higher selective oxidation of HMF to 5-formyl-2-furancarboxylic acid (FFCA) and 2,5-furandicarboxylic acid (FDCA) than with the bases MgO, Ca(OH)₂ and NaOH owing to its appropriate strength of basicity. X-ray photoelectron spectroscopy characterization confirmed that metallic Ru⁰ species were the active sites for HMF oxidation. Isotopic tracer experiments conducted with ¹⁸O₂ and ¹⁶O₂ indicated that H₂O rather than O₂ provided the oxygen atom for the oxidation of HMF to FFCA and FDCA via hydration of the formyl group. These results and kinetic studies of the oxidation of HMF and 2,5-diformylfuran (DFF) led to the proposition that the aerobic oxidation of HMF to FFCA follows a Langmuir-Hinshelwood mechanism. The oxidation involved dissociative adsorption of HMF and O₂ to form adsorbed alcoholate and atomic oxygen species followed by kinetically relevant abstraction of β-H from the alcoholate species via the atomic oxygen species to adsorbed DFF species on the Ru surface, which then underwent hydration and oxidation to FFCA under basic conditions.
- 5-Hydroxymethylfurfural,
- Aerobic oxidation,
- 2,5-Diformylfuran,
- 5-Formyl-2-furancarboxylic acid,
- Hydrotalcite,
- Ruthenium catalyst,
- Reaction mechanism
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沈阳化工大学材料科学与工程学院沈阳 110142