• biomass;
  • green chemistry;
  • hydrolysis;
  • mass spectrometry;
  • oligosaccharides


The use of cellulose is hampered by difficulties with breaking up the biopolymer into soluble products. Herein, we show that the impregnation of cellulosic substrates with catalytic amounts of a strong acid (e.g., H2SO4, HCl) is a highly effective strategy for minimizing the contact problem commonly experienced in mechanically assisted, solid-state reactions. Milling the acid-impregnated cellulose fully converts the substrate into water-soluble oligosaccharides within 2 h. In aqueous solution, soluble products are easily hydrolyzed at 130 °C in 1 h, leading to 91 % conversion of the glucan fraction of α-cellulose into glucose, and 96 % of the xylans into xylose. Minor products are glucose dimers (8 %), 5-hydroxymethylfurfural (1 %) and furfural (4 %). Milling practical feedstocks (e.g., wood, sugarcane bagasse, and switchgrass) also results to water-soluble products (oligosaccharides and lignin fragments). The integrated approach (solid-state depolymerization in combination with liquid-phase hydrolysis) could well hold the key to a highly efficient “entry process” in biorefinery schemes.