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Solvent-enabled control of reactivity for liquid-phase reactions of biomass-derived compounds

Nature Catalysis volume 1, pages 199–207 (2018)Cite this article

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Abstract

The use of organic solvents in biomass conversion reactions can lead to high rates and improved selectivities. Here, we elucidate the effects of organic solvent mixtures with water on the kinetics of acid-catalysed dehydration reactions of relevance to biomass conversion. Based on results from reaction kinetics studies, combined with classical and ab initio molecular dynamics simulations, we show that the rates of acid-catalysed reactions in the liquid phase can be enhanced by altering the extents of solvation of the initial and transition states of these catalytic processes. The extent of these effects increases as the number of vicinal hydroxyl or oxygen-containing groups in the reactant increases, moving from an alcohol (butanol), to a diol (1,2-propanediol), to a carbohydrate (fructose). We demonstrate that the understanding of these solvation effects can be employed to optimize the rate and selectivity for production of the biomass platform molecule hydroxymethylfurfural from fructose.

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Fig. 1: Solvation effects on the kinetics of Brønsted acid-catalysed dehydration reactions.
Fig. 2: DFT simulation results of the Brønsted acid-catalysed dehydration of tert-butanol and 1,2-propanediol.
Fig. 3: Linear relationship between experimentally measured and DFT-calculated apparent activation free energies.
Fig. 4: Reaction kinetics of the consecutive acid-catalysed conversion of fructose to HMF to levulinic acid.

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Acknowledgements

This work was supported in part by the Department of Energy Great Lakes Bioenergy Research Center (https://www.glbrc.org), which is supported by the US Department of Energy, Office of Science, Office of Biological and Environmental Research, through the Cooperative Agreement BER DE-FC02-07ER64494 between The Board of Regents of the University of Wisconsin System and by the National Science Foundation Engineering Research Center for Biorenewable Chemicals (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 US Department of Energy, Office of Basic Energy Sciences (DE-SC0014058). The authors acknowledge the Minnesota Supercomputing Institute (https://www.msi.umn.edu/) at the University of Minnesota for providing resources that contributed to the research results reported within this article. M.N. thanks M. Mahanthappa for helpful discussions.

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Authors and Affiliations

  1. Department of Chemical and Biological Engineering, University of Wisconsin–Madison, Madison, WI, USA

    Max A. Mellmer, Benginur Demir, Kaiwen Ma & James A. Dumesic

  2. DOE Great Lakes Bioenergy Research Center, University of Wisconsin–Madison, Madison, WI, USA

    Max A. Mellmer, Benginur Demir & James A. Dumesic

  3. Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, MN, USA

    Chotitath Sanpitakseree, Peng Bai & Matthew Neurock

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Contributions

M.A.M., B.D. and K.M. carried out the reaction kinetics experiments and analysed the data. C.S. and P.B. performed the molecular dynamics simulations and density functional theory calculations. M.A.M. and J.A.D. conceived the work, and all authors designed and discussed the experimental and computational research. All authors were involved in writing the manuscript.

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Correspondence to James A. Dumesic.

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Supplementary Tables 1–7; Supplementary Discussion; Supplementary Figures 1–24; Supplementary References.

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Mellmer, M.A., Sanpitakseree, C., Demir, B. et al. Solvent-enabled control of reactivity for liquid-phase reactions of biomass-derived compounds. Nat Catal 1, 199–207 (2018). https://doi.org/10.1038/s41929-018-0027-3

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