Protic Br?nsted acidic ionic liquids with variable acidity for efficient conversion of xylose and hemicellulose to furfural

Furfural (FF) is an important platform molecule originated from biomass, but it's synthesis through the tradi-tional acid-catalyzed dehydration reaction of xylose and hemicellulose remains problematic due to the poor activity and equipment corrosion. Therefore, a series of [HSO4]-based protic Bronsted acidic ionic liquids (BAILs) are employed as green catalysts to achieve efficient and sustainable preparation of FF from xylose or hemicel-lulose in this work. Furfural yields of 75.4% or 80.4% were achieved under optimal operating conditions with [Hpy][HSO4] as catalyst, hemicellulose or xylose as substrates, higher than those catalysed with most ionic liquids reported so far. The chemical structures of BAILs were confirmed by NMR and FT-IR spectroscopy, and the Hammett acidity (H0) were determined using UV-vis spectroscopy with 4-nitroaniline as probe. The acidity of BAILs were tuned through methyl substitution on the pyridinium ring, and its effect on the catalysis perfor-mance was investigated. In addition, the reaction constants and the corresponding activation energies of BAILs for dehydration of xylose to FF were calculated by kinetic equations. Overall, the highly efficient catalysis performance, good recyclability and low cost enables [Hpy][HSO4] to be potentially applied for large-scale preparation of FF.