One-pot redox cascade paired electrosynthesis of gamma-butyrolactone from furoic acid

• Published in: Nature communications Vol. 15; no. 1; pp. 1141 - 11
• Main Authors: Liu, Shengqin, Jin, Yangxin, Huang, Shuquan, Zhu, Qi, Shao, Shan, Lam, Jason Chun-Ho
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 07.02.2024; Nature Publishing Group; Nature Portfolio
• Subjects: 140/131; 140/58; 639/638/169; 639/638/224/685; 639/638/77/886; Acids; Aqueous electrolytes; Biomass; Biorefineries; Butyrolactone; Critical temperature; Electrochemistry; Electrolysis; Electrolytes; Furoic acid; Humanities and Social Sciences; multidisciplinary; Nickel; Science; Science (multidisciplinary); Silver chloride; Solvent extraction
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-024-45278-z

The catalytic valorisation of biomass to afford synthetically useful small molecules is essential for sustainable biorefinery processes. Herein, we present a mild cascaded electrochemical protocol for converting furoic acid, a common biomass-derived feedstock, into a versatile platform chemical, gamma-butyrolactone. In the platinum(+)|nickel(−) electrode paired undivided cell, furoic acid is electrochemically oxidised with 84.2% selectivity to 2(5 H )-furanone, the olefin of which is then hydrogenated to yield gamma-butyrolactone with 98.5% selectivity. The final gamma-butyrolactone yield is 69.1% with 38.3% Faradaic efficiency and 80.1% carbon balance when the reaction is performed with 100 mM furoic acid at 80 °C at +2.0 V Ag/AgCl . Mechanistic investigation revealed the critical temperature and electrolyte pH conditions that maximise the production and protection of the key intermediate, furan radical, promoting its transition to 2(5 H )-furanone rather than self-polymerising. The reaction is scalable, as 2.1 g of 98.1% pure gamma-butyrolactone is isolated through a simple solvent extraction. Paired electrolysis is challenging without membrane and redox mediators. The authors developed a one-pot, mediator-free, and scalable e-synthesis of γ-butyrolactone (GBL) from furoic acid with high yield and selectivity in an aqueous electrolyte.