title: Mechanisms and energetics for acid catalyzed β-D-glucose conversion to 5-hydroxymethylfurfurl.
abstract: 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 β-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.
authors.affiliation: Department of Chemical Engineering, University of Arkansas, Fayetteville, Arkansas 72701, United States.
authors.forename: Xianghong
authors.initials: X
authors.lastname: Qian
mesh_terms: D000143:Acids / Q000737:chemistry; D056804:Biofuels; D002384:Catalysis; D002625:Chemistry, Organic; D005662:Furaldehyde / Q000031:analogs & derivatives* / Q000138:chemical synthesis; D005663:Furans / Q000737:chemistry*; D005947:Glucose / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D011522:Protons; D012997:Solvents; D013816:Thermodynamics; D014867:Water / Q000737:chemistry
chemical_list: D000143:Acids; D056804:Biofuels; D005663:Furans; D011522:Protons; D012997:Solvents; D014867:Water; C008046:5-hydroxymethylfurfural; D005662:Furaldehyde; C037555:2,5-dimethylfuran; D005947:Glucose