Bypassing In Situ CO Poisoning in Furfural Conversion: Electron‐Deficient Pd Single‐Atom Alloys Enable One‐Step Selective Synthesis of Tetrahydrofuran
Wuyu Zhao, Song Song, Maofeng Ding, Wei Luo, Landong Li, Xingang Li
Abstract
Abstract The one‐step conversion of biomass‐derived furfural (FUR) to tetrahydrofuran (THF) via combining decarbonylation and hydrogenation offers a sustainable alternative to the industrial Reppe process, while the selectivity control remains a significant challenge. Herein, we identify carbon monoxide (CO), in situ generated during FUR decarbonylation, as a major hindrance, significantly inhibiting subsequent furan hydrogenation. To overcome this limitation, a zeolite‐encapsulated Pt 1 Pd single‐atom alloy (SAA) catalyst, namely Pt 10 Pd 90 @S‐1, is designed, which effectively mitigates CO poisoning and enables efficient FUR conversion to THF, achieving 100% FUR conversion and >93% THF selectivity with good long‐term stability (∼100 h)—among the highest values reported to date. Mechanistic studies reveal that electron‐deficient Pd species adjacent to single Pt atoms in Pt 10 Pd 90 @S‐1 significantly enhance H 2 activation and furan adsorption, enabling efficient hydrogenation at both the C α and C β positions of furan despite CO poisoning. Furthermore, the one‐step process is economically viable with a minimum selling price (MSP) of USD 1701 per tonne of THF, and a life cycle assessment shows a CO 2 equivalent emission of 1.29 tonnes per tonne of THF—less than 25% of that of the traditional Reppe process. This work represents a transformative advancement in sustainable THF production, with the potential to revolutionize industrial THF production.