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Title: Tin-containing zeolites are highly active catalysts for the isomerization of glucose in water

Abstract

The isomerization of glucose into fructose is a large-scale reaction for the production of high-fructose corn syrup (HFCS; reaction performed by enzyme catalysts) and recently is being considered as an intermediate step in the possible route of biomass to fuels and chemicals. Here, it is shown that a large-pore zeolite that contains tin (Sn-Beta) is able to isomerize glucose to fructose in aqueous media with high activity and selectivity. Specifically, a 10% (wt/wt) glucose solution containing a catalytic amount of Sn-Beta (1:50 Sn:glucose molar ratio) gives product yields of approximately 46% (wt/wt) glucose, 31% (wt/wt) fructose, and 9% (wt/wt) mannose after 30 min and 12 min of reaction at 383 K and 413 K, respectively. This reactivity is achieved also when a 45 wt% glucose solution is used. The properties of the large-pore zeolite greatly influence the reaction behavior because the reaction does not proceed with a medium-pore zeolite, and the isomerization activity is considerably lower when the metal centers are incorporated in ordered mesoporous silica (MCM-41). The Sn-Beta catalyst can be used for multiple cycles, and the reaction stops when the solid is removed, clearly indicating that the catalysis is occurring heterogeneously. Most importantly, the Sn-Beta catalyst is ablemore » to perform the isomerization reaction in highly acidic, aqueous environments with equivalent activity and product distribution as in media without added acid. This enables Sn-Beta to couple isomerizations with other acid-catalyzed reactions, including hydrolysis/isomerization or isomerization/dehydration reaction sequences [starch to fructose and glucose to 5-hydroxymethylfurfural (HMF) demonstrated here].« less

Authors:
 [1];  [1];  [1]
  1. California Inst. of Technology (CalTech), Pasadena, CA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC); Catalysis Center for Energy Innovation (CCEI)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1064746
DOE Contract Number:  
SC0001004
Resource Type:
Journal Article
Journal Name:
Proc. Natl. Acad. Sci. U. S. A.
Additional Journal Information:
Journal Volume: 107; Journal Issue: 14; Related Information: CCEI partners with the University of Delaware (lead); Brookhaven National Laboratory; California Institute of Technology; Columbia University; University of Delaware; Lehigh University; University of Massachusetts, Amherst; Massachusetts Institute of Technology; University of Minnesota; Pacific Northwest National Laboratory; University of Pennsylvania; Princeton University; Rutgers University; Journal ID: ISSN 0027--8424
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (homogeneous), catalysis (heterogeneous), biofuels (including algae and biomass), bio-inspired, hydrogen and fuel cells, materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly), synthesis (scalable processing)

Citation Formats

Moliner, Manuel, Roman-Leshkov, Yuriy, and Davis, Mark E. Tin-containing zeolites are highly active catalysts for the isomerization of glucose in water. United States: N. p., 2010. Web. doi:10.1073/pnas.1002358107.
Moliner, Manuel, Roman-Leshkov, Yuriy, & Davis, Mark E. Tin-containing zeolites are highly active catalysts for the isomerization of glucose in water. United States. https://doi.org/10.1073/pnas.1002358107
Moliner, Manuel, Roman-Leshkov, Yuriy, and Davis, Mark E. Tue . "Tin-containing zeolites are highly active catalysts for the isomerization of glucose in water". United States. https://doi.org/10.1073/pnas.1002358107.
@article{osti_1064746,
title = {Tin-containing zeolites are highly active catalysts for the isomerization of glucose in water},
author = {Moliner, Manuel and Roman-Leshkov, Yuriy and Davis, Mark E.},
abstractNote = {The isomerization of glucose into fructose is a large-scale reaction for the production of high-fructose corn syrup (HFCS; reaction performed by enzyme catalysts) and recently is being considered as an intermediate step in the possible route of biomass to fuels and chemicals. Here, it is shown that a large-pore zeolite that contains tin (Sn-Beta) is able to isomerize glucose to fructose in aqueous media with high activity and selectivity. Specifically, a 10% (wt/wt) glucose solution containing a catalytic amount of Sn-Beta (1:50 Sn:glucose molar ratio) gives product yields of approximately 46% (wt/wt) glucose, 31% (wt/wt) fructose, and 9% (wt/wt) mannose after 30 min and 12 min of reaction at 383 K and 413 K, respectively. This reactivity is achieved also when a 45 wt% glucose solution is used. The properties of the large-pore zeolite greatly influence the reaction behavior because the reaction does not proceed with a medium-pore zeolite, and the isomerization activity is considerably lower when the metal centers are incorporated in ordered mesoporous silica (MCM-41). The Sn-Beta catalyst can be used for multiple cycles, and the reaction stops when the solid is removed, clearly indicating that the catalysis is occurring heterogeneously. Most importantly, the Sn-Beta catalyst is able to perform the isomerization reaction in highly acidic, aqueous environments with equivalent activity and product distribution as in media without added acid. This enables Sn-Beta to couple isomerizations with other acid-catalyzed reactions, including hydrolysis/isomerization or isomerization/dehydration reaction sequences [starch to fructose and glucose to 5-hydroxymethylfurfural (HMF) demonstrated here].},
doi = {10.1073/pnas.1002358107},
url = {https://www.osti.gov/biblio/1064746}, journal = {Proc. Natl. Acad. Sci. U. S. A.},
issn = {0027--8424},
number = 14,
volume = 107,
place = {United States},
year = {2010},
month = {4}
}