Highly Efficient Transfer Hydrogenation of Biomass-Derived Furfural to Furfuryl Alcohol over Mesoporous Zr-Containing Hybrids with 5-Sulfosalicylic Acid as a Ligand.

Abstract

The catalytic transfer hydrogenation of biomass-derived furfural to furfuryl alcohol under mild conditions is an attractive topic in biorefinery. Herein, mesoporous Zr-containing hybrids (Zr-hybrids) with a high surface area (281.9–291.3 m2/g) and large pore volume (0.49–0.74 cm3/g) were prepared using the biomass-derived 5-sulfosalicylic acid as a ligand, and they were proven to be highly efficient for the Meerwein–Ponndorf–Verley reduction of furfural to furfuryl alcohol at 110 °C, with the highest furfuryl alcohol yield reaching up to 97.8%. Characterizations demonstrated that sulfonic and carboxyl groups in 5-sulfosalicylic acid molecules were coordinated with zirconium ions, making zirconium ions fully dispersed, thus leading to the formation of very fine zirconia particles with the diameter of <2 nm in mesoporous Zr-hybrids. The interaction between the 5-sulfosalicylic acid ligands and zirconium ions endowed mesoporous Zr-hybrids with relatively higher acid strength but lower base strength, which was beneficial for the selective reduction of furfural to furfuryl alcohol. A recycling study was performed over a certain mesoporous Zr-hybrid, namely meso-Zr-SA15, demonstrating that the yield and selectivity of furfuryl alcohol remained almost unchanged during the five consecutive reaction cycles. This study provides an optional method to prepare hybrid catalysts for biomass refining by using biomass-derived feedstock.