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Mechanisms and Energetics for Brønsted Acid-Catalyzed Glucose Condensation, Dehydration and Isomerization Reactions

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Abstract

The mechanisms and energetics for Brønsted acid-catalyzed glucose condensation, dehydration and isomerization reactions were discussed based on our earlier CPMD–MTD simulation results. Glucose condensation reaction is initiated by the protonation of C1–OH, whereas both dehydration and isomerization reactions are initiated by the protonation of C2–OH to form a common 5-member ring intermediate. Glucose dehydration to form HMF occurs via the direct cyclic mechanism, rather than via the open chain mechanism converting glucose to fructose then to HMF. Fructose is formed via a 1,2 hydride shift process following the formation of 5-member ring intermediate. The barriers for Brønsted acid-catalyzed glucose reactions are largely solvent induced due to the competition for proton from the solvent molecules.

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Acknowledgments

This work is supported by the NSF CAREER (CBET 0844882 and CBET 1137795) and the Department of Energy Office of the Biomass Program via a subcontract from the National Renewable Energy Laboratory (ZCO-7-77386-01). Calculations were carried out on Teragrid and Razor computing facilities from University of Arkansas.

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  1. Department of Chemical Engineering, University of Arkansas, Fayetteville, AR, 72701, USA

    Xianghong Qian

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Qian, X. Mechanisms and Energetics for Brønsted Acid-Catalyzed Glucose Condensation, Dehydration and Isomerization Reactions. Top Catal 55, 218–226 (2012). https://doi.org/10.1007/s11244-012-9790-6

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