Boehmite-supported CuO as a catalyst for catalytic transfer hydrogenation of 5-hydroxymethylfurfural to 2,5-bis(hydroxymethyl)furan

Abstract

2,5-bis(hydroxymethyl)furan (BHMF) is an important monomer of polyester. Its oxygen-containing rigid ring structure and symmetrical diol functional group establish it as an alternative to petroleum-based monomer with unique advantages for the prodution of the degradable bio-based polyester materials. Herein, we prepared a boehmite-supported copper-oxide catalyst for the selective hydrogenation of 5-hydroxymethylfurfural into BHMF via catalytic transfer hydrogenation (CTH). Further, ethanol successfully replaced conventional high-pressure hydrogen as the hydrogen donor, with up to 96.9% BHMF selectivity achieved under suitable conditions. Through characterization and factor investigations, it was noted that CuO is crucial for high BHMF selectivity. Furthermore, kinetic studies revealed a higher by-product activation energy compared to that of BHMF, which explained the influence of reaction temperature on product distribution. To establish the catalyst structure-activity correlation, a possible mechanism was proposed. The copper-oxide catalyst deactivated following CTH because ethanol reduced the CuO, which consequently decreased the active sites. Finally, calcination of the catalyst in air recovered its activity. These results will have a positive impact on hydrogenation processes in the biomass industry.

Graphical abstract

Keywords

biomass / 5-hydroxymethylfurfural / 2,5-bis(hydroxymethyl)furan / transfer hydrogenation / catalysis

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Acknowledgements

The authors gratefully acknowledge the financial support of the National Natural Science Foundation of China (Grant No. 22278121), Scientific Research Fund of Hunan Provincial Education Department (Grant No. 20B364), Hunan Provincial Innovation Foundation for Postgraduate (Grant No. QL20210132), and Science and Technology Planning Project of Hunan Province (Grant Nos. 2021GK5083, 2021GK4049, 2018TP1017).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://dx.doi.org/10.1007/s11705-022-2225-4 and is accessible for authorized users.

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