Differences in Mechanism and Rate of Zeolite-Catalyzed Cyclohexanol Dehydration in Apolar and Aqueous Phase
Abstract
The rate of acid-base catalyzed dehydration of alcohols strongly depends on the solvent and the environment of the acid sites. In this work, we find that Brønsted acidic sites in large-pore zeolites, but not in medium-pore zeolites, catalyze cyclohexanol dehydration in decalin at significantly higher rates than hydrated hydronium ions in aqueous phase. Specifically, the difference in turnover rates between the two solvents amounts to two to three orders of magnitude on H-BEA and H-FAU, while being very modest (within a factor of 2) for H-MFI. Combining kinetic, isotopic tracer and 2H NMR measurements, it is established that cyclohexanol dehydration generally follows an E1-elimination pathway in decalin. A notable exception is the monomer dehydration route on H-MFI, which exhibits a much lower activation energy and a substantially negative activation entropy that appear to be associated with an E2-type mechanism. The C-O bond cleavage displays a dominant degree of rate control in decalin, which stands in contrast to deprotonation (C-H cleavage) being rate-limiting in aqueous-phase dehydration.
- Authors:
-
[1];
[1];
[1];
[2];
[1];
[1];
[3]
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Technische Univ. Munchen, Garching (Germany)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Technische Univ. Munchen, Garching (Germany)
- Publication Date:
- Research Org.:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Biological and Environmental Research (BER)
- OSTI Identifier:
- 1781124
- Report Number(s):
- PNNL-SA-159842
Journal ID: ISSN 2155-5435
- Grant/Contract Number:
- AC05-76RL01830
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 5; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Alcohol dehydration; Solid-liquid interface; Confinement effect; Zeolites; Elimination mechanism
Citation Formats
Chen, Feng, Shetty, Manish, Wang, Meng, Shi, Hui, Liu, Yuanshuai, Camaioni, Donald M., Gutiérrez, Oliver Y., and Lercher, Johannes A. Differences in Mechanism and Rate of Zeolite-Catalyzed Cyclohexanol Dehydration in Apolar and Aqueous Phase. United States: N. p., 2021.
Web. doi:10.1021/acscatal.0c05674.
Chen, Feng, Shetty, Manish, Wang, Meng, Shi, Hui, Liu, Yuanshuai, Camaioni, Donald M., Gutiérrez, Oliver Y., & Lercher, Johannes A. Differences in Mechanism and Rate of Zeolite-Catalyzed Cyclohexanol Dehydration in Apolar and Aqueous Phase. United States. https://doi.org/10.1021/acscatal.0c05674
Chen, Feng, Shetty, Manish, Wang, Meng, Shi, Hui, Liu, Yuanshuai, Camaioni, Donald M., Gutiérrez, Oliver Y., and Lercher, Johannes A. Wed .
"Differences in Mechanism and Rate of Zeolite-Catalyzed Cyclohexanol Dehydration in Apolar and Aqueous Phase". United States. https://doi.org/10.1021/acscatal.0c05674. https://www.osti.gov/servlets/purl/1781124.
@article{osti_1781124,
title = {Differences in Mechanism and Rate of Zeolite-Catalyzed Cyclohexanol Dehydration in Apolar and Aqueous Phase},
author = {Chen, Feng and Shetty, Manish and Wang, Meng and Shi, Hui and Liu, Yuanshuai and Camaioni, Donald M. and Gutiérrez, Oliver Y. and Lercher, Johannes A.},
abstractNote = {The rate of acid-base catalyzed dehydration of alcohols strongly depends on the solvent and the environment of the acid sites. In this work, we find that Brønsted acidic sites in large-pore zeolites, but not in medium-pore zeolites, catalyze cyclohexanol dehydration in decalin at significantly higher rates than hydrated hydronium ions in aqueous phase. Specifically, the difference in turnover rates between the two solvents amounts to two to three orders of magnitude on H-BEA and H-FAU, while being very modest (within a factor of 2) for H-MFI. Combining kinetic, isotopic tracer and 2H NMR measurements, it is established that cyclohexanol dehydration generally follows an E1-elimination pathway in decalin. A notable exception is the monomer dehydration route on H-MFI, which exhibits a much lower activation energy and a substantially negative activation entropy that appear to be associated with an E2-type mechanism. The C-O bond cleavage displays a dominant degree of rate control in decalin, which stands in contrast to deprotonation (C-H cleavage) being rate-limiting in aqueous-phase dehydration.},
doi = {10.1021/acscatal.0c05674},
journal = {ACS Catalysis},
number = 5,
volume = 11,
place = {United States},
year = {Wed Feb 17 00:00:00 EST 2021},
month = {Wed Feb 17 00:00:00 EST 2021}
}
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