Bypassing In Situ CO Poisoning in Furfural Conversion: Electron‐Deficient Pd Single‐Atom Alloys Enable One‐Step Selective Synthesis of Tetrahydrofuran

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.