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Title: Directing the Rate‐Enhancement for Hydronium Ion Catalyzed Dehydration via Organization of Alkanols in Nanoscopic Confinements

Abstract

Alkanol dehydration rates catalyzed by hydronium ions are enhanced by the dimensions of steric confinements of zeolite pores as well as by intraporous intermolecular interactions with other alkanols. The higher rates with zeolite MFI having pores smaller than those of zeolite BEA for dehydration of secondary alkanols, 3-heptanol and 2-methyl-3-hexanol, is caused by the lower activation enthalpy in the tighter confinements of MFI that offsets a less positive activation entropy. The higher activity in BEA than in MFI for dehydration of a tertiary alkanol, 2-methyl-2-hexanol, is primarily attributed to the reduction of the activation enthalpy by stabilizing intraporous interactions of the Cß-H transition state with surrounding alcohol molecules. Overall, we show that the positive impact of zeolite confinements results from the stabilization of transition state provided by the confinement and intermolecular interaction of alkanols with the transition state, which is impacted by both the size of confines and structure of alkanols in the E1 pathway of dehydration.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [3]
  1. Institute of Integrated Catalysis Pacific Northwest National Laboratory (PNNL) P.O. Box 999 Richland WA 99352 USA
  2. Department of Chemistry and Catalysis Research Center Technical University München Lichtenbergstrasse 4 85747 München Germany
  3. Institute of Integrated Catalysis Pacific Northwest National Laboratory (PNNL) P.O. Box 999 Richland WA 99352 USA, Department of Chemistry and Catalysis Research Center Technical University München Lichtenbergstrasse 4 85747 München Germany
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1724439
Alternate Identifier(s):
OSTI ID: 1775487; OSTI ID: 1786186
Report Number(s):
PNNL-SA-156707
Journal ID: ISSN 1433-7851
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Published Article
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition) Journal Volume: 60 Journal Issue: 5; Journal ID: ISSN 1433-7851
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; aliphatic alcohols; confinement effect; enthalpy-entropy compensation; hydronium ion; zeolites

Citation Formats

Shetty, Manish, Wang, Huamin, Chen, Feng, Jaegers, Nicholas, Liu, Yue, Camaioni, Donald M., Gutiérrez, Oliver Y., and Lercher, Johannes A.. Directing the Rate‐Enhancement for Hydronium Ion Catalyzed Dehydration via Organization of Alkanols in Nanoscopic Confinements. Germany: N. p., 2020. Web. https://doi.org/10.1002/anie.202009835.
Shetty, Manish, Wang, Huamin, Chen, Feng, Jaegers, Nicholas, Liu, Yue, Camaioni, Donald M., Gutiérrez, Oliver Y., & Lercher, Johannes A.. Directing the Rate‐Enhancement for Hydronium Ion Catalyzed Dehydration via Organization of Alkanols in Nanoscopic Confinements. Germany. https://doi.org/10.1002/anie.202009835
Shetty, Manish, Wang, Huamin, Chen, Feng, Jaegers, Nicholas, Liu, Yue, Camaioni, Donald M., Gutiérrez, Oliver Y., and Lercher, Johannes A.. Fri . "Directing the Rate‐Enhancement for Hydronium Ion Catalyzed Dehydration via Organization of Alkanols in Nanoscopic Confinements". Germany. https://doi.org/10.1002/anie.202009835.
@article{osti_1724439,
title = {Directing the Rate‐Enhancement for Hydronium Ion Catalyzed Dehydration via Organization of Alkanols in Nanoscopic Confinements},
author = {Shetty, Manish and Wang, Huamin and Chen, Feng and Jaegers, Nicholas and Liu, Yue and Camaioni, Donald M. and Gutiérrez, Oliver Y. and Lercher, Johannes A.},
abstractNote = {Alkanol dehydration rates catalyzed by hydronium ions are enhanced by the dimensions of steric confinements of zeolite pores as well as by intraporous intermolecular interactions with other alkanols. The higher rates with zeolite MFI having pores smaller than those of zeolite BEA for dehydration of secondary alkanols, 3-heptanol and 2-methyl-3-hexanol, is caused by the lower activation enthalpy in the tighter confinements of MFI that offsets a less positive activation entropy. The higher activity in BEA than in MFI for dehydration of a tertiary alkanol, 2-methyl-2-hexanol, is primarily attributed to the reduction of the activation enthalpy by stabilizing intraporous interactions of the Cß-H transition state with surrounding alcohol molecules. Overall, we show that the positive impact of zeolite confinements results from the stabilization of transition state provided by the confinement and intermolecular interaction of alkanols with the transition state, which is impacted by both the size of confines and structure of alkanols in the E1 pathway of dehydration.},
doi = {10.1002/anie.202009835},
journal = {Angewandte Chemie (International Edition)},
number = 5,
volume = 60,
place = {Germany},
year = {2020},
month = {11}
}

Journal Article:
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https://doi.org/10.1002/anie.202009835

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