Issue 48, 2012
From the journal:

Physical Chemistry Chemical Physics

Glucose and fructose to platform chemicals: understanding the thermodynamic landscapes of acid-catalysed reactions using high-level ab initio methods†

Rajeev S. Assary,*ab   Taejin Kim,c   John J. Low,d   Jeff Greeleye  and  Larry A. Curtiss*ae  

* Corresponding authors

a Materials Science Division, Argonne National Laboratory, IL, Argonne, USA
E-mail: assary@anl.gov
Fax: +1 011-630-252-9555
Tel: +1 011-630-252-7020

b Chemical & Biological Engineering, Northwestern University, IL, Evanston, USA
E-mail: curtiss@anl.gov
Fax: +1 011-630-252-9555
Tel: +1 011-630-252-7380

c Chemical Science and Engineering Division, Argonne National Laboratory, IL, Argonne, USA

d Argonne Leadership Computing Facility, Argonne National Laboratories, IL, Argonne, USA

e Center for Nanoscale Materials, Argonne National Laboratory, Argonne, IL, USA

Abstract

Molecular level understanding of acid-catalysed conversion of sugar molecules to platform chemicals such as hydroxy-methyl furfural (HMF), furfuryl alcohol (FAL), and levulinic acid (LA) is essential for efficient biomass conversion. In this paper, the high-level G4MP2 method along with the SMD solvation model is employed to understand detailed reaction energetics of the acid-catalysed decomposition of glucose and fructose to HMF. Based on protonation free energies of various hydroxyl groups of the sugar molecule, the relative reactivity of gluco-pyranose, fructo-pyranose and fructo-furanose are predicted. Calculations suggest that, in addition to the protonated intermediates, a solvent assisted dehydration of one of the fructo-furanosyl intermediates is a competing mechanism, indicating the possibility of multiple reaction pathways for fructose to HMF conversion in aqueous acidic medium. Two reaction pathways were explored to understand the thermodynamics of glucose to HMF; the first one is initiated by the protonation of a C2–OH group and the second one through an enolate intermediate involving acyclic intermediates. Additionally, a pathway is proposed for the formation of furfuryl alcohol from glucose initiated by the protonation of a C2–OH position, which includes a C–C bond cleavage, and the formation of formic acid. The detailed free energy landscapes predicted in this study can be used as benchmarks for further exploring the sugar decomposition reactions, prediction of possible intermediates, and finally designing improved catalysts for biomass conversion chemistry in the future.

Graphical abstract: Glucose and fructose to platform chemicals: understanding the thermodynamic landscapes of acid-catalysed reactions using high-level ab initio methods

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Article information

DOI
https://doi.org/10.1039/C2CP41842H
Article type
Paper
Submitted
01 Jun 2012
Accepted
07 Aug 2012
First published
07 Aug 2012

Phys. Chem. Chem. Phys., 2012,14, 16603-16611

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Glucose and fructose to platform chemicals: understanding the thermodynamic landscapes of acid-catalysed reactions using high-level ab initio methods

R. S. Assary, T. Kim, J. J. Low, J. Greeley and L. A. Curtiss, Phys. Chem. Chem. Phys., 2012, 14, 16603 DOI: 10.1039/C2CP41842H

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