Efficient base-free oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid over copper-doped manganese oxide nanorods with tert-butanol as solvent

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.

Graphical abstract

Keywords

5-hydroxymethylfurfural 2,5-furandicarboxylic acid / selective oxidation / Cu-doped MnO₂ / biomass transformation

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Acknowledgements

The authors gratefully acknowledge the financial support of the National Natural Science Foundation of China (Grant No. 21606082), Hunan Provincial Natural Science Foundation of China (No. 2018JJ3334), China Postdoctoral Science Foundation (No. 2019M662787), and Hunan Provincial Innovation Foundation for Postgraduate (No. CX20200522).

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