One-pot domino conversion of biomass-derived furfural to γ-valerolactone with an in-situ formed bifunctional catalyst

ABSTRACT

γ-Valerolactone (GVL) is widely used as a green solvent and in the generation of liquid fuels. GVL can be obtained from biomass-derived furanic compounds through a cascade reaction process, which is extremely challenging due to the need for different active sites in a single pot. Here, we reported a domino conversion process of directly upgrading furfural (FF) to GVL in isopropanol over a commercially available and budget catalyst ZrCl₄ that can in-situ release Brønsted acid (HCl) and Lewis acid/base species (ZrO(OH)_n·xH₂O). The in-situ formed bifunctional catalyst can significantly enable twice transfer hydrogenation, etherification, the ring-opening, and cyclization reactions, giving a high GVL yield of 56.5% from FF at 180°C for 6 h. In addition, the solid residues collected after reaction could be calcined to obtain t-ZrO₂-(C) nanoparticles with a rough surface, in which the insoluble humin attached to the hydrolyzed solid was demonstrated to improve the layered aggregate structure of the resulting t-ZrO₂-(C). Interestingly, t-ZrO₂-(C) showed good performance in catalytic conversion of FF to furfuryl alcohol (FAOL) with ca. 80% yield. The developed bifunctional and recyclable catalytic system exhibits potential for one-pot multi-step biomass valorization.

KEYWORDS:

• Biomass conversion
• biofuels
• furfural
• γ-valerolactone
• transfer hydrogenation

Disclosure statement

No potential conflict of interest was reported by the author(s).

Additional information

Funding

Financial supports from the National Natural Science Foundation of China (21908033, 21576059, 21666008), Fok Ying-Tong Education Foundation (161030), the Program of Introducing Talents of Discipline to Universities of China (111 Program, D20023), and Guizhou Frontiers Science Center for Asymmetric Synthesis and Medicinal Molecules ([2020]004) are warmly acknowledged;Fok Ying Tong Education Foundation [161030].

Notes on contributors

Xialing Lin

Xialing Lin: B.S. in Chemistry (Anyang Normal University, China). Currently, she is an M.S. candidate at Guizhou University under the supervision of Prof. Hu Li. Her research focuses on renewable energy and heterogeneous catalysis.

Mingrui Li

Mingrui Li: B.S. in Applied Chemistry (Southwest Minzu University, China). Currently, she is an M.S. candidate at Guizhou University under the supervision of Prof. Hu Li. Her research focuses on renewable energy and heterogeneous catalysis.

Yumei Jian

Yumei Jian: B.S. in Chemistry (Zunyi Normal University, China). Currently, she is an M.S. candidate at Guizhou University under the supervision of Prof. Hu Li. Her research focuses on renewable energy and heterogeneous catalysis.

Jinshu Huang

Jinshu Huang: B.S. in Chemical Engineering and Technology (Anshun University, China) in 2020. Currently, she is a M.S. candidate at Guizhou University under the supervision of Prof. Hu Li. Her research focuses on renewable energy and heterogeneous catalysis.

Song Yang

Song Yang: Professor at Guizhou University, China. He obtained his PhD from Guizhou University in 2005, and accepted a post-doctoral position in the University of Texas Southwestern Medical Center at Dallas, USA. He was awarded with China National ‘Ten-Thousand-Talent Plan’ and Distinguished Professor of Cheung Kong Scholars Program. His research interests include biofuels, discovery of new agrochemicals, and nanomaterials. Prof. Yang has authored over 50 patents and more than 300 scientific papers in international journals. He is currently Editor-in-Chief of Current Catalysis, and Associate Editor of Current Nanoscience.

Hu Li

Hu Li: Professor of Center for R&D of Fine Chemicals, Guizhou University (GZU), China. Dr. Li stayed as a visiting student researcher at Technical University of Denmark, and University of Chinese Academy of Sciences prior to obtaining his Ph.D. from GZU. He then worked as a postdoctoral fellow at Nanjing Agricultural University (China), and Tohoku University (Japan). His research focuses on the catalytic conversion of renewable and waste resources into chemicals and biofuels with functional materials. Dr. Li has published more than 10 patents and over 100 peer-reviewed papers, and edited 4 books. Currently, He is Associate Editor of Frontiers in Energy Research, and Current Green Chemistry, and Editorial Board Member of several international journals.