The Alpha–Bet(a) of Salty Glucose Pyrolysis: Computational Investigations Reveal Carbohydrate Pyrolysis Catalytic Action by Sodium Ions

Abstract

Biomass pyrolysis is a promising technology for the production of renewable fuels and chemicals from nonfood biomass. Given the potential of pyrolysis as a viable, cost-effective biomass deconstruction method, there is active interest in understanding the chemical transformations at the heart of the technology. It has long been known that the presence of alkali- and alkaline-earth-metal ions in biomass, such as Na+, significantly alters product yields of biomass pyrolysis, but the mechanism behind this effect has not been elucidated. In this work, we employ density functional theory (DFT) to reveal the stereoelectronic basis of the effect of sodium ions on several key glucose thermal decomposition reactions, such as the formation of levoglucosan and 5-hydroxymethylfurfural (5-HMF). β-d-Glucose is of interest for pyrolysis, as it is the monomer of cellulose and a key intermediate in cellulose pyrolysis. α-d-Glucose is included in this study, as the two anomers can readily interconvert under pyrolysis condi...