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Published April 6, 2010 | Supplemental Material + Published
Journal Article Open

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 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].

Additional Information

© 2010 by the National Academy of Sciences. Freely available online through the PNAS open access option. Contributed by Mark E. Davis, February 24, 2010 (sent for review February 14, 2010). Published online before print March 22, 2010. This work was financially supported as part of the Catalysis Center for Energy Innovation, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC00010004. M.M. acknowledges the Fundación Ramón Areces Postdoctoral Research Fellowship Program for financial support. Author contributions: Y.R.-L., M.M., and M.E.D. designed research; M.M. performed research; Y.R.-L., M.M., and M.E.D. analyzed data; and Y.R.-L., M.M., and M.E.D. wrote the paper.

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Published - Moliner2010p9843P_Natl_Acad_Sci_Usa.pdf

Supplemental Material - Appendix.pdf

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August 21, 2023
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