Insights on the efficiency of bifunctional solid organocatalysts in converting xylose and biomass into furfural in a GVL-water solvent

A bifunctional solid organocatalyst, sulfamic acid, was evaluated to produce furfural from xylose and different biomass in an environmentally friendly system comprising Gamma-Valerolactone (GVL) and water. The highest yield (70.19%) of furfural was achieved in a 90% solution of GVL in water containing 10 mol% of sulfamic acid at 190 °C for 15 min from xylose. The potential mechanism of sulfamic acid efficiently catalyzing xylose isomerization and dehydration is presented for the first time. It is hypothesized that another sulfamic acid form, the zwitterionic unit (H₃N⁺SO₃ ⁻) is crucial in efficiently catalyzing isomerization reaction due to its electron-rich sulfonate being superior in attacking the hydrogen atom on C1 leading to the xylose tautomerization to xylulose, a shorter route to furfural, and finally, the NH₂SO₃H with strong acidity also promotes the xylulose dehydration to furfural. The above system was evaluated using various biomass species including corncob, Miscanthus × giganteus, the hull and shell of Camellia oleifera (tea) fruit and Aleurites fordii HemsL. (tung) fruit. Almost all these biomass showed excellent furfural yields (over 70%), with tung shell providing the best yield of 92.19% at 200 °C and reaction time of 30 min.