Mechanisms and Energetics for Acid Catalyzed beta-D-Glucose Conversion to 5-Hydroxymethylfurfurl

作者：Qian Xianghong^*

来源：Journal of Physical Chemistry A, 2011, 115(42): 11740-11748.

DOI：10.1021/jp2041982

Car-Parrinello based ab initio molecular dynamics (CPMD) coupled with metadynamics (MTD) simulations were carried out to investigate the mechanism and energetics for acid-catalyzed beta-D-glucose conversion to 5-hydroxymethylfurfurl (HMF) in water. HMF is a critical intermediate for biomass conversion to biofuels. It was found that protonation of the C2-OH on glucose, the breakage of the C2-O2 bond, and the formation of the C2-O5 bond is the critical rate-limiting step for the direct glucose conversion to HMF without converting to fructose first, contrary to the wide-spread assumption in literature that fructose is the main intermediate for glucose conversion to HMF. The calculated reaction barrier of 30-35 kcal/mol appears to be solvent-induced and is in excellent agreement with experimental observations.

• 出版日期2011-10-27