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; James A. Dumesic

doi:10.1038/s41467-019-09090-4

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, James A. Dumesic

Research output: Contribution to journal › Article › peer-review

87 Scopus citations

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.

Original language	English (US)
Article number	1132
Journal	Nature Communications
Volume	10
Issue number	1
DOIs	https://doi.org/10.1038/s41467-019-09090-4
State	Published - Dec 1 2019
Externally published	Yes

ASJC Scopus subject areas

Chemistry(all)
Biochemistry, Genetics and Molecular Biology(all)
Physics and Astronomy(all)

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10.1038/s41467-019-09090-4

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@article{e8915f693b1a42d5bb0f43a47c072e0a,

title = "Effects of chloride ions in acid-catalyzed biomass dehydration reactions in polar aprotic solvents",

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 Br{\o}nsted 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.",

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

note = "Funding Information: This material is based upon work supported in part by the Great Lakes Bioenergy Research Center, U.S. Department of Energy, Office of Science, and Office of Biological and Environmental Research under Award Numbers DE-SC0018409 and DE-FC02–07ER64494. W.A.E. and R.M.R. acknowledge funding from the Department of Energy, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, and Catalysis Sciences Program under grant number DE-SC0016192. Further support was provided in part by the National Science Foundation Engineering Research Center for Biorenewable Chemicals (CBiRC; https://www.cbirc.iastate.edu) under Award No. EEC-0813570. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Science Foundation. J.A.D. was supported by the U.S. Department of Energy, Office of Basic Energy Sciences (DE-SC0014058). The authors acknowledge the Environmental Molecular Sciences Laboratory (EMSL) and the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for the computational resources to carry out the simulations. Publisher Copyright: {\textcopyright} 2019, The Author(s).",

year = "2019",

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doi = "10.1038/s41467-019-09090-4",

language = "English (US)",

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T1 - Effects of chloride ions in acid-catalyzed biomass dehydration reactions in polar aprotic solvents

AU - Mellmer, Max A.

AU - Sanpitakseree, Chotitath

AU - Demir, Benginur

AU - Ma, Kaiwen

AU - Elliott, William A.

AU - Bai, Peng

AU - Johnson, Robert L.

AU - Walker, Theodore W.

AU - Shanks, Brent H.

AU - Rioux, Robert M.

AU - Neurock, Matthew

AU - Dumesic, James A.

N1 - Funding Information: This material is based upon work supported in part by the Great Lakes Bioenergy Research Center, U.S. Department of Energy, Office of Science, and Office of Biological and Environmental Research under Award Numbers DE-SC0018409 and DE-FC02–07ER64494. W.A.E. and R.M.R. acknowledge funding from the Department of Energy, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, and Catalysis Sciences Program under grant number DE-SC0016192. Further support was provided in part by the National Science Foundation Engineering Research Center for Biorenewable Chemicals (CBiRC; https://www.cbirc.iastate.edu) under Award No. EEC-0813570. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Science Foundation. J.A.D. was supported by the U.S. Department of Energy, Office of Basic Energy Sciences (DE-SC0014058). The authors acknowledge the Environmental Molecular Sciences Laboratory (EMSL) and the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for the computational resources to carry out the simulations. Publisher Copyright: © 2019, The Author(s).

PY - 2019/12/1

Y1 - 2019/12/1

N2 - 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.

AB - 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.

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JO - Nature Communications

JF - Nature Communications

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ER -

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

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