Mechanistic insights into the decomposition of fructose to hydroxy methyl furfural in neutral and acidic environments using high-level quantum chemical methods.

Journal Article · Mon Mar 28 04:00:00 EDT 2011 · J. Phys. Chem. B

DOI:https://doi.org/10.1021/jp1104278· OSTI ID:1012808

Assary, R S; Redfern, P C; Greeley, J; Curtiss, L A ^[1]

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1. Center for Nanoscale Materials

Efficient catalytic chemical transformation of fructose to hydroxy methyl furfural (HMF) is one of the key steps for attaining industrial level conversion of biomass to useful chemicals. We report an investigation of the reaction mechanisms for the decomposition of fructose to HMF in both neutral and acidic environments at the Gaussian-4 level of theory including calculation of enthalpies, free energies, and effective solvation interactions. In neutral water solvent, the transformation of fructose to HMF involves a four step reaction sequence with four transition states. The effective activation energy relative to fructose in neutral water at 298 K is very large, about 74 kcal/mol, so that transformation in neutral media around this temperature is unlikely. In contrast, the computed potential energy surface is much more favorable for the transformation in acidic media at 498 K, as the effective activation barrier is about 39 kcal/mol. The transformation in acidic media is a much more complex mechanism involving dehydration and hydrogen transfer steps, which are more favorable when protonated intermediates are involved.

• Research Organization: Argonne National Laboratory (ANL)
• Sponsoring Organization: SC
• DOE Contract Number: AC02-06CH11357
• OSTI ID: 1012808
• Report Number(s): ANL/MSD/JA-69658
• Journal Information: J. Phys. Chem. B, Journal Name: J. Phys. Chem. B Journal Issue: Mar. 28, 2011 Vol. 115; ISSN 1089-5647
• Country of Publication: United States
• Language: ENGLISH

Related Subjects

09 BIOMASS FUELS
ACTIVATION ENERGY
BIOMASS
DEHYDRATION
FRUCTOSE
FURFURAL
HYDROGEN TRANSFER
POTENTIAL ENERGY
REACTION KINETICS
SOLVATION
TRANSFORMATIONS
WATER