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Title: Comparison of sugar molecule decomposition through glucose and fructose: a high-level quantum chemical study.

Abstract

Efficient chemical conversion of biomass is essential to produce sustainable energy and industrial chemicals. Industrial level conversion of glucose to useful chemicals, such as furfural, hydroxymethylfurfural, and levulinic acid, is a major step in the biomass conversion but is difficult because of the formation of undesired products and side reactions. To understand the molecular level reaction mechanisms involved in the decomposition of glucose and fructose, we have carried out high-level quantum chemical calculations [Gaussian-4 (G4) theory]. Selective 1,2-dehydration, keto-enol tautomerization, isomerization, retro-aldol condensation, and hydride shifts of glucose and fructose molecules were investigated. Detailed kinetic and thermodynamic analyses indicate that, for acyclic glucose and fructose molecules, the dehydration and isomerization require larger activation barriers compared to the retro-aldol reaction at 298 K in neutral medium. The retro-aldol reaction results in the formation of C2 and C4 species from glucose and C3 species from fructose. The formation of the most stable C3 species, dihydroxyacetone from fructose, is thermodynamically downhill. The 1,3-hydride shift leads to the cleavage of the C-C bond in the acyclic species; however, the enthalpy of activation is significantly higher (50-55 kcal/mol) than that of the retro-aldol reaction (38 kcal/mol) mainly because of the sterically hindered distorted four-membered transitionmore » state compared to the hexa-membered transition state in the retro-aldol reaction. Both tautomerization and dehydration are catalyzed by a water molecule in aqueous medium; however, water has little effect on the retro-aldol reaction. Isomerization of glucose to fructose and glyceraldehyde to dihydroxyacetone proceeds through hydride shifts that require an activation enthalpy of about 40 kcal/mol at 298 K in water medium. This investigation maps out accurate energetics of the decomposition of glucose and fructose molecules that is needed to help find more efficient catalysts for the conversion of hexose to useful chemicals.« less

Authors:
;  [1]
  1. Center for Nanoscale Materials
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1042584
Report Number(s):
ANL/MSD/JA-73536
Journal ID: ISSN 0887-0624; TRN: US201212%%859
DOE Contract Number:  
DE-AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Energy Fuels
Additional Journal Information:
Journal Volume: 26; Journal Issue: 2; Journal ID: ISSN 0887-0624
Country of Publication:
United States
Language:
ENGLISH
Subject:
09 BIOMASS FUELS; BIOMASS; C4 SPECIES; CATALYSTS; CLEAVAGE; DEHYDRATION; ENTHALPY; FRUCTOSE; FURFURAL; GLUCOSE; HEXOSES; HYDRIDES; ISOMERIZATION; KINETICS; LEVULINIC ACID; REACTION KINETICS; SACCHAROSE; THERMODYNAMICS; WATER

Citation Formats

Assary, R S, Curtiss, L A, MSD), and Northwestern Univ.). Comparison of sugar molecule decomposition through glucose and fructose: a high-level quantum chemical study.. United States: N. p., 2012. Web. doi:10.1021/ef201654s.
Assary, R S, Curtiss, L A, MSD), & Northwestern Univ.). Comparison of sugar molecule decomposition through glucose and fructose: a high-level quantum chemical study.. United States. https://doi.org/10.1021/ef201654s
Assary, R S, Curtiss, L A, MSD), and Northwestern Univ.). 2012. "Comparison of sugar molecule decomposition through glucose and fructose: a high-level quantum chemical study.". United States. https://doi.org/10.1021/ef201654s.
@article{osti_1042584,
title = {Comparison of sugar molecule decomposition through glucose and fructose: a high-level quantum chemical study.},
author = {Assary, R S and Curtiss, L A and MSD) and Northwestern Univ.)},
abstractNote = {Efficient chemical conversion of biomass is essential to produce sustainable energy and industrial chemicals. Industrial level conversion of glucose to useful chemicals, such as furfural, hydroxymethylfurfural, and levulinic acid, is a major step in the biomass conversion but is difficult because of the formation of undesired products and side reactions. To understand the molecular level reaction mechanisms involved in the decomposition of glucose and fructose, we have carried out high-level quantum chemical calculations [Gaussian-4 (G4) theory]. Selective 1,2-dehydration, keto-enol tautomerization, isomerization, retro-aldol condensation, and hydride shifts of glucose and fructose molecules were investigated. Detailed kinetic and thermodynamic analyses indicate that, for acyclic glucose and fructose molecules, the dehydration and isomerization require larger activation barriers compared to the retro-aldol reaction at 298 K in neutral medium. The retro-aldol reaction results in the formation of C2 and C4 species from glucose and C3 species from fructose. The formation of the most stable C3 species, dihydroxyacetone from fructose, is thermodynamically downhill. The 1,3-hydride shift leads to the cleavage of the C-C bond in the acyclic species; however, the enthalpy of activation is significantly higher (50-55 kcal/mol) than that of the retro-aldol reaction (38 kcal/mol) mainly because of the sterically hindered distorted four-membered transition state compared to the hexa-membered transition state in the retro-aldol reaction. Both tautomerization and dehydration are catalyzed by a water molecule in aqueous medium; however, water has little effect on the retro-aldol reaction. Isomerization of glucose to fructose and glyceraldehyde to dihydroxyacetone proceeds through hydride shifts that require an activation enthalpy of about 40 kcal/mol at 298 K in water medium. This investigation maps out accurate energetics of the decomposition of glucose and fructose molecules that is needed to help find more efficient catalysts for the conversion of hexose to useful chemicals.},
doi = {10.1021/ef201654s},
url = {https://www.osti.gov/biblio/1042584}, journal = {Energy Fuels},
issn = {0887-0624},
number = 2,
volume = 26,
place = {United States},
year = {Wed Feb 01 00:00:00 EST 2012},
month = {Wed Feb 01 00:00:00 EST 2012}
}