Effects of chloride ions in acid-catalyzed biomass dehydration reactions in polar aprotic solvents

Max A. Mellmer, Chotitath Sanpitakseree, Benginur Demir, Kaiwen Ma, William A. Elliott, Peng Bai, Robert L. Johnson, Theodore W. Walker, Brent H. Shanks, Robert M. Rioux, Matthew Neurock and James A. Dumesic ()
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Max A. Mellmer: University of Wisconsin–Madison
Chotitath Sanpitakseree: University of Minnesota
Benginur Demir: University of Wisconsin–Madison
Kaiwen Ma: University of Wisconsin–Madison
William A. Elliott: Pennsylvania State University
Peng Bai: University of Minnesota
Robert L. Johnson: Iowa State University
Theodore W. Walker: University of Wisconsin–Madison
Brent H. Shanks: Iowa State University
Robert M. Rioux: Pennsylvania State University
Matthew Neurock: University of Minnesota
James A. Dumesic: University of Wisconsin–Madison

Nature Communications, 2019, vol. 10, issue 1, 1-10

Abstract: Abstract The use of polar aprotic solvents in acid-catalyzed biomass conversion reactions can lead to improved reaction rates and selectivities. We show that further increases in catalyst performance in polar aprotic solvents can be achieved through the addition of inorganic salts, specifically chlorides. Reaction kinetics studies of the Brønsted acid-catalyzed dehydration of fructose to hydroxymethylfurfural (HMF) show that the use of catalytic concentrations of chloride salts leads to a 10-fold increase in reactivity. Furthermore, increased HMF yields can be achieved using polar aprotic solvents mixed with chlorides. Ab initio molecular dynamics simulations (AIMD) show that highly localized negative charge on Cl− allows the chloride anion to more readily approach and stabilize the oxocarbenium ion that forms and the deprotonation transition state. High concentrations of polar aprotic solvents form local hydrophilic environments near the reactive hydroxyl group which stabilize both the proton and chloride anions and promote the dehydration of fructose.

Date: 2019
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DOI: 10.1038/s41467-019-09090-4

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