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

Mellmer, Max A.; Sanpitakseree, Chotitath; Demir, Benginur; Ma, Kaiwen; Elliott, William A.; Bai, Peng; Johnson, Robert L.; Walker, Theodore W.; Shanks, Brent H.; Rioux, Robert M.; Neurock, Matthew; Dumesic, James A.

doi:10.1038/s41467-019-09090-4

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

Journal Article · Fri Mar 08 00:00:00 EST 2019 · Nature Communications

DOI:https://doi.org/10.1038/s41467-019-09090-4· OSTI ID:1548298

Mellmer, Max A. ^[1]; Sanpitakseree, Chotitath ^[2];

^[3]; Ma, Kaiwen ^[4]; Elliott, William A. ^[5];

^[2]; Johnson, Robert L. ^[6]; Walker, Theodore W. ^[4]; Shanks, Brent H. ^[6]; Rioux, Robert M. ^[5]; Neurock, Matthew ^[2];

^[3]

University of Wisconsin–Madison, Madison, WI (United States); USDOE Great Lakes Bioenergy Research Center, Madison, WI (United States)
Univ. of Minnesota, Minneapolis, MN (United States)
University of Wisconsin–Madison, Madison, WI (United States); USDOE Great Lakes Bioenergy Research Center, Madison, WI (United States)
University of Wisconsin–Madison, Madison, WI (United States)
Pennsylvania State Univ., University Park, PA (United States)
Iowa State Univ., Ames, IA (United States)

The utilization of polar aprotic solvents in acid-catalyzed biomass conversion reactions can lead to improved reaction rates and selectivities. We demonstrate 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.

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Research Organization:: Great Lakes Bioenergy Research Center (GLBRC), Madison, WI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Science Foundation (NSF); Minnesota Supercomputing Institute (MSI)

Grant/Contract Number:: SC0018409; FC02–07ER64494; SC0016192; SC0014058; EEC-0813570

OSTI ID:: 1548298

Journal Information:: Nature Communications, Vol. 10, Issue 1; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 92 works

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