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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

Postal Subscription Code 80-969

2018 Impact Factor: 2.809

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Front. Chem. Sci. Eng.    2021, Vol. 15 Issue (4) : 960-968    https://doi.org/10.1007/s11705-020-1999-5
RESEARCH ARTICLE
Efficient base-free oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid over copper-doped manganese oxide nanorods with tert-butanol as solvent
Feng Cheng, Dongwen Guo, Jinhua Lai, Meihui Long, Wenguang Zhao, Xianxiang Liu(), Dulin Yin
National & Local Joint Engineering Laboratory for New Petro-chemical Materials and Fine Utilization of Resources, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, China
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Abstract

2,5-Furandicarboxylic acid (FDCA) is an important and renewable building block and can serve as an alternative to terephthalic acid in the production of bio-based degradable plastic. In this study, Cu-doped MnO2 nanorods were prepared by a facile hydrothermal redox method and employed as catalysts for the selective oxidation of 5-hydroxymethylfurfural (HMF) to FDCA using tert-butyl hydroperoxide (TBHP) as an oxidant. The catalysts were characterized using X-ray diffraction analysis, Fourier transform infrared spectroscopy, thermogravimetric analysis, and transmission electron microscopy. The effects of oxidants, solvents, and reaction conditions on the oxidation of HMF were investigated, and a reaction mechanism was proposed. Experimental results demonstrated that 99.4% conversion of HMF and 96.3% selectivity of FDCA were obtained under suitable conditions, and tert-butanol was the most suitable solvent when TBHP was used as an oxidant. More importantly, the Cu-doped MnO2 catalyst can maintain durable catalytic activity after being recycled for more than ten times.
Keywords 5-hydroxymethylfurfural 2,5-furandicarboxylic acid      selective oxidation      Cu-doped MnO2      biomass transformation     
Corresponding Author(s): Xianxiang Liu   
Just Accepted Date: 20 November 2020   Online First Date: 08 January 2021    Issue Date: 04 June 2021
 Cite this article:   
Feng Cheng,Dongwen Guo,Jinhua Lai, et al. Efficient base-free oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid over copper-doped manganese oxide nanorods with tert-butanol as solvent[J]. Front. Chem. Sci. Eng., 2021, 15(4): 960-968.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-020-1999-5
https://academic.hep.com.cn/fcse/EN/Y2021/V15/I4/960
Fig.1  Scheme 1 Two?possible?pathways?for the oxidation?of?HMF?to FDCA.
Fig.2  Scheme 2 Schematic for the synthesis of polyethylene furanoate (PEF) from biomass-derived carbohydrates.
Fig.3  XRD patterns of the MnO2 and Cu-doped MnO2 catalysts.
Fig.4  FTIR spectra of the MnO2 and Cu-doped MnO2 catalysts.
Fig.5  TG curve of the MnO2 and Cu-doped MnO2 catalysts.
Fig.6  (a) TEM image of the Cu-doped MnO2 nanorods and (b) MnO2 nanorods, (c) HRTEM image of the Cu-doped MnO2 nanorods, and (d) a nanorod showing [110] lattice fringes.
Fig.7  (a) Elemental maps and (b) HAADF-STEM image of the Cu-doped MnO2 catalyst, and?elemental maps of (c) Cu, (d) Mn, (e) O.
Entry Catalysts Conversion/% Selectivity/%
FDCA FFCA DFF Others
1 None 45.3 14.8 59.7 23.1 2.4
2 MnO2 92.5 85.2 13.2 0.7 0.9
3 Cu-doped MnO2 99.4 96.3 3.1 0.4 0.2
Tab.1  Effects of catalysts on the oxidation of HMF a)
Entry Oxidants Conversion/% Selectivity/%
FDCA FFCA DFF Others
1 O2b) 56.8 2.6 23.6 72.7 1.0
2 H2O2c) 34.2 0.4 5.3 93.0 1.3
3 TBHP d) 99.4 96.3 3.1 0.4 0.2
Tab.2  Effects of oxidants on the oxidation of HMF a)
Fig.8  Effects of solvents on the oxidation of HMF. Reaction conditions: HMF (0.1 mmol), Cu-doped MnO2 (20 mg), solvent (5 mL), 80 °C, 12 h, and 0.9 mL TBHP as an oxidant.
Fig.9  Decomposition rate of TBHP in H2O and TBA. Reaction conditions: solvent (5 mL), 80 °C, 12 h, and 0.9 mL TBHP.
Fig.10  Effects of the H2O to TBA volume ratio on the oxidation of HMF. Reaction conditions: HMF (0.1 mmol), Cu-doped MnO2 (20 mg), 80 °C, 12 h, and 0.9 mL TBHP as an oxidant.
Fig.11  Time course of HMF oxidation over the Cu-doped MnO2 catalyst. Reaction conditions: HMF (0.1 mmol), Cu-doped MnO2 (20 mg), TBA (8 mL), 80 °C, and 0.9 mL TBHP as an oxidant.
Fig.12  Results of the reusability test of Cu-doped MnO2. Reaction conditions: HMF (0.1 mmol), Cu-doped MnO2 (20 mg), TBA (5 mL), 80 °C, 6 h, and 0.9 mL TBHP as an oxidant.
Fig.13  Proposed reaction mechanism for the selective oxidation of HMF to FDCA over Cu-doped MnO2.
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