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Title: Tailoring nanoscopic confines to maximize catalytic activity of hydronium ions

Abstract

Acid catalysis by hydronium ions, such as aqueous phase dehydration of cyclohexanol, is markedly influenced by the steric nano-environments, enhancing catalytic activity by as much as two orders of magnitude. In contrast to Brønsted-acid-catalyzed gas-phase alcohol elimination reactions, hydronium ions catalyze cyclohexanol dehydration to cyclohexene via an E1-type elimination path with the cleavage of a Cß–H bond in the carbenium-ion as the rate-determining step. The higher catalytic activity of hydronium ions in zeolites with smaller pores is caused mainly by lower activation barriers in such tighter pore confines, which are partly offset by less positive activation entropies. The molecularly sized pores also significantly enhance the association between intraporous hydronium ions and alcohols, leading to a specific binding usually only found in enzymes. This work was supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Portions of the NMR experiments were performed at the William R. Environmental Molecular Science Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research located at Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for DOE by Battelle Memorial Institute.

Authors:
ORCiD logo [1];  [2];  [1]; ORCiD logo [1]; ORCiD logo [3]
+ Show Author Affiliations
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis
  2. Technische Univ. Munchen, Garching (Germany). Dept. of Chemistry and Catalysis Research Center
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis; Technische Univ. Munchen, Garching (Germany). Dept. of Chemistry and Catalysis Research Center
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1623891
Alternate Identifier(s):
OSTI ID: 1735943
Report Number(s):
PNNL-SA-121731
Journal ID: ISSN 2041-1723; PII: BFncomms15442
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; alcohol dehydration; biomass conversion; zeolite; cyclohexanol; water; transition states

Citation Formats

Shi, Hui, Eckstein, Sebastian, Vjunov, Aleksei, Camaioni, Donald M., and Lercher, Johannes A. Tailoring nanoscopic confines to maximize catalytic activity of hydronium ions. United States: N. p., 2017. Web. doi:10.1038/ncomms15442.
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Shi, Hui, Eckstein, Sebastian, Vjunov, Aleksei, Camaioni, Donald M., & Lercher, Johannes A. Tailoring nanoscopic confines to maximize catalytic activity of hydronium ions. United States. https://doi.org/10.1038/ncomms15442
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Shi, Hui, Eckstein, Sebastian, Vjunov, Aleksei, Camaioni, Donald M., and Lercher, Johannes A. Thu . "Tailoring nanoscopic confines to maximize catalytic activity of hydronium ions". United States. https://doi.org/10.1038/ncomms15442. https://www.osti.gov/servlets/purl/1623891.
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@article{osti_1623891,
title = {Tailoring nanoscopic confines to maximize catalytic activity of hydronium ions},
author = {Shi, Hui and Eckstein, Sebastian and Vjunov, Aleksei and Camaioni, Donald M. and Lercher, Johannes A.},
abstractNote = {Acid catalysis by hydronium ions, such as aqueous phase dehydration of cyclohexanol, is markedly influenced by the steric nano-environments, enhancing catalytic activity by as much as two orders of magnitude. In contrast to Brønsted-acid-catalyzed gas-phase alcohol elimination reactions, hydronium ions catalyze cyclohexanol dehydration to cyclohexene via an E1-type elimination path with the cleavage of a Cß–H bond in the carbenium-ion as the rate-determining step. The higher catalytic activity of hydronium ions in zeolites with smaller pores is caused mainly by lower activation barriers in such tighter pore confines, which are partly offset by less positive activation entropies. The molecularly sized pores also significantly enhance the association between intraporous hydronium ions and alcohols, leading to a specific binding usually only found in enzymes. This work was supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Portions of the NMR experiments were performed at the William R. Environmental Molecular Science Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research located at Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for DOE by Battelle Memorial Institute.},
doi = {10.1038/ncomms15442},
journal = {Nature Communications},
number = 1,
volume = 8,
place = {United States},
year = {Thu May 25 00:00:00 EDT 2017},
month = {Thu May 25 00:00:00 EDT 2017}
}
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https://doi.org/10.1038/ncomms15442
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    Works referencing / citing this record:

    The Nature and Catalytic Function of Cation Sites in Zeolites: a Computational Perspective
    journal, October 2018

    Influence of Hydronium Ions in Zeolites on Sorption
    journal, March 2019

    • Eckstein, Sebastian; Hintermeier, Peter H.; Zhao, Ruixue
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    Influence of Hydronium Ions in Zeolites on Sorption
    journal, March 2019

    • Eckstein, Sebastian; Hintermeier, Peter H.; Zhao, Ruixue
    • Angewandte Chemie International Edition, Vol. 58, Issue 11
    • DOI: 10.1002/anie.201812184
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