Mechanistic understanding of salt-assisted autocatalytic hydrolysis of cellulose

Depolymerisation of cellulose is a critical step for biomass-based bio-refining processes to produce valuable chemicals. Herein, we propose the mechanism of the promoting effect of NaCl on the cellulose hydrolysis process based on a systematic kinetic study involving variable temperature studies and the use of deuterated agents. It has been found that the presence of NaCl simultaneously enhances the generation of acidic products from cellulose decomposition and pushes the generated protons to the surface of cellulose, dramatically increasing surface acidity and facilitating the autocatalytic hydrolysis of cellulose. Cl- disrupted the intermolecular hydrogen bonding of cellulose, especially in the first surface layer. Thus, the solid cellulose chains were peeled off layer-by-layer, leading to an accelerated hydrolysis of cellulose by the adsorbed protons. Without the need for traditional acidic catalysts, this autocatalytic depolymerisation of cellulose in water, assisted by salt provides a practically viable route to the enhanced conversion of biomass to chemicals.