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Title: Tandem Aromatization of Oxygenated Furans by Framework Zinc In Zeolites. A Computational Study

Abstract

We have performed electronic structure calculations to characterize the active site of the zeolite CIT-6 (isomorphically substituted Zn-Beta) and to study the Diels–Alder dehydrative aromatization of methyl-5-(methoxymethyl)-furoate (MMFC) and of the dimethyl ester of 2,5-furan-dicarboxylic acid (DMFDC) with ethylene. Three types of active sites have been investigated: a site where the framework charge was balanced by two protons (Z0); a site with an H+ and a Li+ as counter-cations (Z1); and an active site with two Li+ counter-cations (Z2). Using NBO and Bader analysis, we conclude that Zn incorporation into the zeolite framework is not through covalent bonding to framework oxygen atoms but rather is through ionic bonding. Despite the ionic character of the active site and the generally strong Lewis acidic nature of Zn(II) cations, we find no catalysis of the Diels–Alder reaction for the two furans tested. On the other hand, the dehydration of the Diels–Alder cycloadduct can be either Brønsted or Lewis acid catalyzed depending on the active site type. The Z0-type sites are found to be more active than the Z1- and Z2-type sites. Furthermore, the Z0-type sites exhibit both Lewis and Brønsted acid characters with similar catalytic activities. In full agreement with experiment, we findmore » that the conversion of MMFC to (4-methoxymethyl) benzenecarboxylate via Diels–Alder dehydrative aromatization is easier than the conversion of DMFDC to dimethyl terephthalate as the two electron withdrawing groups in DMFDC stabilize the corresponding cycloadduct against dehydration.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
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  1. Univ. of Delaware, Newark, DE (United States). Dept. of Chemical and Biomolecular Engineering, and Catalysis Center for Energy Innovation (CCEI)
  2. Univ. of Delaware, Newark, DE (United States). Catalysis Center for Energy Innovation (CCEI)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1482393
Grant/Contract Number:  
SC0001004; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 40; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Patet, Ryan E., Caratzoulas, Stavros, and Vlachos, Dionisios G. Tandem Aromatization of Oxygenated Furans by Framework Zinc In Zeolites. A Computational Study. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b07402.
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Patet, Ryan E., Caratzoulas, Stavros, & Vlachos, Dionisios G. Tandem Aromatization of Oxygenated Furans by Framework Zinc In Zeolites. A Computational Study. United States. https://doi.org/10.1021/acs.jpcc.7b07402
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Patet, Ryan E., Caratzoulas, Stavros, and Vlachos, Dionisios G. Fri . "Tandem Aromatization of Oxygenated Furans by Framework Zinc In Zeolites. A Computational Study". United States. https://doi.org/10.1021/acs.jpcc.7b07402. https://www.osti.gov/servlets/purl/1482393.
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@article{osti_1482393,
title = {Tandem Aromatization of Oxygenated Furans by Framework Zinc In Zeolites. A Computational Study},
author = {Patet, Ryan E. and Caratzoulas, Stavros and Vlachos, Dionisios G.},
abstractNote = {We have performed electronic structure calculations to characterize the active site of the zeolite CIT-6 (isomorphically substituted Zn-Beta) and to study the Diels–Alder dehydrative aromatization of methyl-5-(methoxymethyl)-furoate (MMFC) and of the dimethyl ester of 2,5-furan-dicarboxylic acid (DMFDC) with ethylene. Three types of active sites have been investigated: a site where the framework charge was balanced by two protons (Z0); a site with an H+ and a Li+ as counter-cations (Z1); and an active site with two Li+ counter-cations (Z2). Using NBO and Bader analysis, we conclude that Zn incorporation into the zeolite framework is not through covalent bonding to framework oxygen atoms but rather is through ionic bonding. Despite the ionic character of the active site and the generally strong Lewis acidic nature of Zn(II) cations, we find no catalysis of the Diels–Alder reaction for the two furans tested. On the other hand, the dehydration of the Diels–Alder cycloadduct can be either Brønsted or Lewis acid catalyzed depending on the active site type. The Z0-type sites are found to be more active than the Z1- and Z2-type sites. Furthermore, the Z0-type sites exhibit both Lewis and Brønsted acid characters with similar catalytic activities. In full agreement with experiment, we find that the conversion of MMFC to (4-methoxymethyl) benzenecarboxylate via Diels–Alder dehydrative aromatization is easier than the conversion of DMFDC to dimethyl terephthalate as the two electron withdrawing groups in DMFDC stabilize the corresponding cycloadduct against dehydration.},
doi = {10.1021/acs.jpcc.7b07402},
journal = {Journal of Physical Chemistry. C},
number = 40,
volume = 121,
place = {United States},
year = {2017},
month = {9}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1021/acs.jpcc.7b07402
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Cited by: 8 works
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Figures / Tables:

Scheme 1 Scheme 1: Dehydrative aromatization of furans.
All figures and tables (11 total)
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Works referenced in this record:

The Conservation of Orbital Symmetry
journal, November 1969

  • Woodward, R. B.; Hoffmann, Roald
  • Angewandte Chemie International Edition in English, Vol. 8, Issue 11
  • DOI: 10.1002/anie.196907811

Self-Pillared, Single-Unit-Cell Sn-MFI Zeolite Nanosheets and Their Use for Glucose and Lactose Isomerization
journal, July 2015

  • Ren, Limin; Guo, Qiang; Kumar, Prashant
  • Angewandte Chemie International Edition, Vol. 54, Issue 37
  • DOI: 10.1002/anie.201505334

Supramolecular Binding Thermodynamics by Dispersion-Corrected Density Functional Theory
journal, July 2012

Update of the AIM2000-Program for atoms in molecules: Update of the AIM2000-Program for Atoms in Molecules
journal, October 2002

  • Biegler-König, Friedrich; Schönbohm, Jens
  • Journal of Computational Chemistry, Vol. 23, Issue 15
  • DOI: 10.1002/jcc.10085
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    Works referencing / citing this record:

    Formaldehyde–isobutene Prins condensation over MFI-type zeolites
    journal, January 2018

    • Vasiliadou, Efterpi S.; Li, Sha; Caratzoulas, Stavros
    • Catalysis Science & Technology, Vol. 8, Issue 22
    • DOI: 10.1039/c8cy01667d
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      Figures / Tables found in this record:

      Scheme 1 (p. 11)figure
      Scheme 2 (p. 12)figure
      Figure 1 (p. 13)figure
      Figure 2 (p. 14)figure
      Figure 3 (p. 15)figure
      Figure 4 (p. 16)figure
      Figure 5 (p. 17)figure
      Scheme 3 (p. 18)figure
      Figure 6 (p. 19)figure
      Table 1 (p. 20)table
      Table 2 (p. 21)table
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        Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

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