Efficient Conversion of Glucose to 5-Hydroxymethylfurfural over a Sn-Modified SAPO-34 Zeolite Catalyst

Efficient and one-pot conversion of biomass-derived carbohydrate into highly value-added 5-hydroxymethylfurfural (HMF) is a crucial reaction step for the valorization of biomass resources toward bio-based chemicals and fuels. In this work, a series of Sn/SAPO-34 catalysts were prepared through impregnation and evaluated in glucose conversion to HMF. The physicochemical properties of Sn/SAPO-34 catalysts were systematically characterized by SEM, XRD, N-2 physisorption, XPS, solid-state Sn-119, Si-29, and P-31 NMR, XRF, UV-vis, NH3-TPD, and pyridine-FTIR techniques. It was demonstrated that controlling the Sn loading amount could facilely adjust the acid strength and acid amount of the SAPO-34 zeolite. The incorporation of Sn species could induce the formation of a tetrahedrally coordinated Sn4+ site and Sn-OH site to improve the amounts of Bronsted and Lewis acid sites of the catalyst. However, modification with sufficiently high Sn loading could decrease the acid strength and performance of the catalyst owing to its structure damage. The 5%Sn/SAPO-34 catalyst (i.e., Sn loading calculated based on the mass ratio of SnCl4 center dot 5H(2)O as a precursor to the parent SAPO-34) was found to exhibit the superior catalytic performance under mild conditions and could afford an HMF yield of 64.4% at 98.5% glucose conversion in a biphasic 35 wt % NaCl-H2O/tetrahydrofuran (THF) system at 150 degrees C within 1.5 h. Additionally, a catalytic reaction pathway was proposed, involving the adsorption of glucose molecules by the -Cl group on the catalyst via a hydrogen bond, followed by glucose isomerization to fructose over the Lewis acid Sn4+ and Al3+ sites and, finally, fructose dehydration to HMF catalyzed by the Bronsted acid Sn-OH and Si-OH-Al sites. The activity of the catalyst decreased due to the leaching of the active site Sn after several consecutive cycles. This work provides insights into the improvement in the Sn-containing zeolite catalyst for tandem conversion of glucose to HMF.

Automated summary

Efficient conversion of biomass-derived carbohydrates into highly value-added 5-hydroxymethylfurfural (HMF) using Sn/SAPO-34 catalysts was investigated. Control of Sn loading amount could adjust acid strength and amount in the catalyst, while excessively high loading would decrease performance due to structure damage. The 5%Sn/SAPO-34 catalyst showed superior performance in achieving high HMF yield from glucose conversion.