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Title: Mechanism of Phenol Alkylation in Zeolite H-BEA Using In Situ Solid-State NMR Spectroscopy

Abstract

Alkylation of phenolic compounds in the liquid phase is of fundamental and practical importance to the conversion of biomass-derived feedstocks into fuels and chemicals. In this work, the reaction mechanism for phenol alkylation with cyclohexanol and cyclohexene has been investigated on a commercial HBEA zeolite by in situ 13C MAS NMR, using decalin as the solvent. From the variable temperature 13C MAS NMR measurements of phenol and cyclohexanol adsorption on HBEA from decalin solutions, it is shown that the two molecules have similar adsorption strength in the HBEA pore. Phenol alkylation with cyclohexanol, however, becomes significantly measurable only after cyclohexanol is largely converted to cyclohexene via dehydration. This is in contrast to the initially rapid alkylation of phenol when using cyclohexene as the co-reactant. 13C isotope scrambling results demonstrate that the electrophile, presumably cyclohexyl carbenium ion, is directly formed in a protonation step when cyclohexene is the co-reactant, but requires re-adsorption of the alcohol dehydration product, cyclohexene, when cyclohexanol dimer is the dominant surface species (e.g., at 0.5 M cyclohexanol concentration) that is unable to generate carbenium ion. At the initial reaction stage of phenol-cyclohexanol alkylation on HBEA, the presence of the cyclohexanol dimer species hinders the adsorption of cyclohexenemore » at the Brønsted acid site and the subsequent activation of the more potent electrophile (carbenium ion). Isotope scrambling data also show that intramolecular rearrangement of cyclohexyl phenyl ether, the O-alkylation product, does not significantly contribute to the formation of C-alkylation products.« less

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1];  [1];  [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [3]
  1. Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, United States
  2. Department of Chemistry and Catalysis Research Center, TU München, Lichtenbergstrasse 4, 85748 Garching, Germany
  3. Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, United States; Department of Chemistry and Catalysis Research Center, TU München, Lichtenbergstrasse 4, 85748 Garching, Germany
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1372006
Report Number(s):
PNNL-SA-122818
Journal ID: ISSN 0002-7863; 48810; KC0302010
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society; Journal Volume: 139; Journal Issue: 27
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Environmental Molecular Sciences Laboratory

Citation Formats

Zhao, Zhenchao, Shi, Hui, Wan, Chuan, Hu, Mary Y., Liu, Yuanshuai, Mei, Donghai, Camaioni, Donald M., Hu, Jian Zhi, and Lercher, Johannes A. Mechanism of Phenol Alkylation in Zeolite H-BEA Using In Situ Solid-State NMR Spectroscopy. United States: N. p., 2017. Web. doi:10.1021/jacs.7b02153.
Zhao, Zhenchao, Shi, Hui, Wan, Chuan, Hu, Mary Y., Liu, Yuanshuai, Mei, Donghai, Camaioni, Donald M., Hu, Jian Zhi, & Lercher, Johannes A. Mechanism of Phenol Alkylation in Zeolite H-BEA Using In Situ Solid-State NMR Spectroscopy. United States. doi:10.1021/jacs.7b02153.
Zhao, Zhenchao, Shi, Hui, Wan, Chuan, Hu, Mary Y., Liu, Yuanshuai, Mei, Donghai, Camaioni, Donald M., Hu, Jian Zhi, and Lercher, Johannes A. Tue . "Mechanism of Phenol Alkylation in Zeolite H-BEA Using In Situ Solid-State NMR Spectroscopy". United States. doi:10.1021/jacs.7b02153.
@article{osti_1372006,
title = {Mechanism of Phenol Alkylation in Zeolite H-BEA Using In Situ Solid-State NMR Spectroscopy},
author = {Zhao, Zhenchao and Shi, Hui and Wan, Chuan and Hu, Mary Y. and Liu, Yuanshuai and Mei, Donghai and Camaioni, Donald M. and Hu, Jian Zhi and Lercher, Johannes A.},
abstractNote = {Alkylation of phenolic compounds in the liquid phase is of fundamental and practical importance to the conversion of biomass-derived feedstocks into fuels and chemicals. In this work, the reaction mechanism for phenol alkylation with cyclohexanol and cyclohexene has been investigated on a commercial HBEA zeolite by in situ 13C MAS NMR, using decalin as the solvent. From the variable temperature 13C MAS NMR measurements of phenol and cyclohexanol adsorption on HBEA from decalin solutions, it is shown that the two molecules have similar adsorption strength in the HBEA pore. Phenol alkylation with cyclohexanol, however, becomes significantly measurable only after cyclohexanol is largely converted to cyclohexene via dehydration. This is in contrast to the initially rapid alkylation of phenol when using cyclohexene as the co-reactant. 13C isotope scrambling results demonstrate that the electrophile, presumably cyclohexyl carbenium ion, is directly formed in a protonation step when cyclohexene is the co-reactant, but requires re-adsorption of the alcohol dehydration product, cyclohexene, when cyclohexanol dimer is the dominant surface species (e.g., at 0.5 M cyclohexanol concentration) that is unable to generate carbenium ion. At the initial reaction stage of phenol-cyclohexanol alkylation on HBEA, the presence of the cyclohexanol dimer species hinders the adsorption of cyclohexene at the Brønsted acid site and the subsequent activation of the more potent electrophile (carbenium ion). Isotope scrambling data also show that intramolecular rearrangement of cyclohexyl phenyl ether, the O-alkylation product, does not significantly contribute to the formation of C-alkylation products.},
doi = {10.1021/jacs.7b02153},
journal = {Journal of the American Chemical Society},
number = 27,
volume = 139,
place = {United States},
year = {Tue Jun 27 00:00:00 EDT 2017},
month = {Tue Jun 27 00:00:00 EDT 2017}
}