Insight into the formation mechanism of levoglucosenone in phosphoric acid-catalyzed fast pyrolysis of cellulose

The catalytic fast pyrolysis of cellulose impregnated with phosphoric acid (H 3 PO 4 ) offers a promising method for the selective production of levoglucosenone (LGO), a valuable anhydrosugar product. However, the fundamental mechanism for selective LGO formation is unclear. Herein, quantum chemistry calculations and catalytic fast pyrolysis experiments were performed to reveal the formation mechanism of LGO in H 3 PO 4 -catalyzed cellulose pyrolysis. H 3 PO 4 significantly decreased the energy barriers of the pyrolytic reactions and altered the competitiveness of the LGO formation pathways, promoting LGO formation. Through different pathways in the non-catalytic and H 3 PO 4 -catalyzed conditions, LGO is mainly produced from the primary decomposition of glucose units of cellulose and secondary conversion of levoglucosan. The major catalytic formation pathways of LGO comprise similar reactions, with dehydration at the 3-OH + 2-H site as the rate-determining step. Importantly, secondary conversion of 1,4;3,6-dianhydro-α- d -glucopyranose is not feasible for LGO formation, in contrast to previous reports. In addition, a high degree of polymerization is beneficial for the selectivity of LGO formation in the catalytic process, because the glycosidic bond is important for the formation of the bicyclic structure (1,5- and 1,6-acetal rings).