Dual acidic mesoporous KIT silicates enable one-pot production of γ-valerolactone from biomass derivatives via cascade reactions. (February 2020)

• Record Type: Journal Article
• Authors: He, Jian; Li, Hu; Xu, Yufei; Yang, Song
• Is Part Of: Renewable energy. Volume 146(2020)
• Page Start: 359
• Page End: 370
• Publication Date: 2020-02
• Subjects: Biomass conversion -- Mesoporous silicate -- γ-Valerolactone -- Furfural -- Transfer hydrogenation; Renewable energy sources -- Periodicals; Power resources -- Periodicals; Énergies renouvelables -- Périodiques; Ressources énergétiques -- Périodiques; 333.794
• DOI: 10.1016/j.renene.2019.06.105
• Languages: English
• ISSNs: 0960-1481

Abstract

Abstract: γ-Valerolactone (GVL) is an interesting bio-based platform molecule that is utilized as green solvent and a versatile building block for the synthesis of bio-fuels and chemicals. Herein, an investigation on the efficient production of GVL from biomass-based carbonyl compounds such as furfural, levulinic acid, and its esters using 2-propanol as H-donor and solvent over stable Zr-incorporated mesoporous silica (KIT-5) catalysts was presented. Both Lewis and Brønsted acid sites were generated by the introduction of Zr into KIT-5, and the acid density of the resulting Zr-KIT-5(Si/Zr) could be controlled by simply adjusting Si/Zr molar ratio. Among these bifunctional catalysts, Zr-KIT-5(10) showed superior catalytic performance in the production of GVL (>91% selectivity) from biomass-derived carboxides (ca. 94% conversion), which was demonstrated to positively correlate with its large amount of acidic sites and facile access of active sites to interconnected pores. Moreover, the spent catalyst held about 90% of its original activity in the sixth run. Due to the presence of Brønsted and Lewis dual acidic sites in Zr-KIT-5, the direct conversion of furfural to GVL was also permitted in a single pot via tandem reactions involving hydrogenation, ring-opening, secondary hydrogenation, and subsequent cyclization. Graphical abstract: Image 1 Highlights: Zr-KIT-5 with dual Brønsted-Lewis acid sites were prepared by a facile method. Zr-KIT-5 catalysts were efficient for selective upgrading of bio-based levulinates. A high selectivity to γ -valerolactone (>91%) was obtained over Zr-KIT-5(10). Zr-KIT-5(10) preserved ∼90% of its original activity after six consecutive cycles. Zr-KIT-5(10) could catalyze one-pot conversion of furfural to γ -valerolactone.