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Tailoring nanoscopic confines to maximize catalytic activity of hydronium ions

Author

Listed:
  • Hui Shi

    (Institute for Integrated Catalysis, Pacific Northwest National Laboratory)

  • Sebastian Eckstein

    (Department of Chemistry and Catalysis Research Center)

  • Aleksei Vjunov

    (Institute for Integrated Catalysis, Pacific Northwest National Laboratory)

  • Donald M. Camaioni

    (Institute for Integrated Catalysis, Pacific Northwest National Laboratory)

  • Johannes A. Lercher

    (Institute for Integrated Catalysis, Pacific Northwest National Laboratory
    Department of Chemistry and Catalysis Research Center)

Abstract

Acid catalysis by hydronium ions is ubiquitous in aqueous-phase organic reactions. Here we show that hydronium ion catalysis, exemplified by intramolecular dehydration of cyclohexanol, is markedly influenced by steric constraints, yielding turnover rates that increase by up to two orders of magnitude in tight confines relative to an aqueous solution of a Brønsted acid. The higher activities in zeolites BEA and FAU than in water are caused by more positive activation entropies that more than offset higher activation enthalpies. The higher activity in zeolite MFI with pores smaller than BEA and FAU is caused by a lower activation enthalpy in the tighter confines that more than offsets a less positive activation entropy. Molecularly sized pores significantly enhance the association between hydronium ions and alcohols in a steric environment resembling the constraints in pockets of enzymes stabilizing active sites.

Suggested Citation

  • Hui Shi & Sebastian Eckstein & Aleksei Vjunov & Donald M. Camaioni & Johannes A. Lercher, 2017. "Tailoring nanoscopic confines to maximize catalytic activity of hydronium ions," Nature Communications, Nature, vol. 8(1), pages 1-7, August.
    • Handle: RePEc:nat:natcom:v:8:y:2017:i:1:d:10.1038_ncomms15442
    DOI: 10.1038/ncomms15442
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    Cited by:

    1. Gomes, Glaucio J. & Costa, Michelle Budke & Bittencourt, Paulo R.S. & Zalazar, María Fernanda & Arroyo, Pedro A., 2021. "Catalytic improvement of biomass conversion: Effect of adding mesoporosity on MOR zeolite for esterification with oleic acid," Renewable Energy, Elsevier, vol. 178(C), pages 1-12.

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