High-temperature decomposition of amorphous and crystalline cellulose: reactive molecular simulations

Abstract We study the thermal decomposition of cellulose using molecular simulations based on ReaxFF reactive force field. Our analysis focuses mechanism and kinetics chain scission, their sensitivity condensed phase environment. For this purpose, we simulate amorphous partially crystalline at various heating rates. find that degradation begins with depolymerization via glycosidic bond cleavage, order events corresponds to a randomly initiated reaction. Depolymerization is followed by ring fragmentation reactions lead formation number light oxygenates. Water formed mainly in intermolecular dehydration later stage. The reaction rate cleavage follows sigmoidal model, an apparent activation energy 166 ± 4 kJ/mol. Neither environment nor programme have appreciable effects reactions. make several observations are compatible mechanisms proposed for fast pyrolysis. However, due absence anhydrosugar forming reactions, offer limited insight conditions industrial interest. It remains unclear whether natural consequence conditions, or shortcoming field its parameter set. Graphic abstract