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Title: Entrapped Single Tungstate Site in Zeolite for Cooperative Catalysis of Olefin Metathesis with Brønsted Acid Site

Abstract

Industrial olefin metathesis catalysts generally suffer from low reaction rates and require harsh reaction conditions for moderate activities. This is due to their inability to prevent metathesis active sites (MAS) from aggregation and their intrinsic poor adsorption and activation of olefin molecules. Here, isolated tungstate species as single molecular MAS is immobilized inside zeolite pores by Bronsted acid sites (BAS) on the inner surface. It is demonstrated for the first time that unoccupied BAS in atomic proximity to MAS enhance olefin adsorption and greatly facilitate the formation of metallocycle intermediates in a stereospecific manner. Thus, effective cooperative catalysis takes place over the BAS-MAS pair. In consequence, for the cross-metathesis of ethene and trans-2-butene to propene, under the same mild reaction conditions, the propene production rate over WOx/USY is ca. 7,300 times that over the industrial WO3/SiO2 based catalyst. A propene yield up to 79% (80% selectivity) without observable deactivation was obtained over WOx/USY for a wide range of reaction conditions.

Authors:
 [1];  [1]; ORCiD logo [1];  [1];  [1];  [2];  [3];  [4]; ORCiD logo [5]; ORCiD logo [1]
  1. Wolfson Catalysis Centre, Department of Chemistry, University of Oxford, Oxford OX1 3QR, U.K.
  2. Department of Materials, University of Oxford, Oxford OX1 3PH, U.K.
  3. Diamond Light Source Ltd., Harwell Science and Innovation Campus, Didcot OX11 0DE, U.K.
  4. Department of Materials, University of Oxford, Oxford OX1 3PH, U.K.; Diamond Light Source Ltd., Harwell Science and Innovation Campus, Didcot OX11 0DE, U.K.
  5. Physical and Computational Sciences Directorate &, Institute for Integrated Catalysis, Pacific Northwest National Laboratory, PO Box 999, Richland, Washington 99354, United States
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1455312
Report Number(s):
PNNL-SA-134054
Journal ID: ISSN 0002-7863; 49734; KC0302010
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society; Journal Volume: 140; Journal Issue: 21
Country of Publication:
United States
Language:
English
Subject:
Metathesis; Isolated Tungstate site; Zeolites; Density functional theory; Reaction pathway; Brønsted acid sites; Environmental Molecular Sciences Laboratory

Citation Formats

Zhao, Pu, Ye, Lin, Sun, Zhenyu, Lo, Benedict T. W., Woodcock, Harry, Huang, Chen, Tang, Chiu, Kirkland, Angus I., Mei, Donghai, and Edman Tsang, Shik Chi. Entrapped Single Tungstate Site in Zeolite for Cooperative Catalysis of Olefin Metathesis with Brønsted Acid Site. United States: N. p., 2018. Web. doi:10.1021/jacs.8b03012.
Zhao, Pu, Ye, Lin, Sun, Zhenyu, Lo, Benedict T. W., Woodcock, Harry, Huang, Chen, Tang, Chiu, Kirkland, Angus I., Mei, Donghai, & Edman Tsang, Shik Chi. Entrapped Single Tungstate Site in Zeolite for Cooperative Catalysis of Olefin Metathesis with Brønsted Acid Site. United States. doi:10.1021/jacs.8b03012.
Zhao, Pu, Ye, Lin, Sun, Zhenyu, Lo, Benedict T. W., Woodcock, Harry, Huang, Chen, Tang, Chiu, Kirkland, Angus I., Mei, Donghai, and Edman Tsang, Shik Chi. Mon . "Entrapped Single Tungstate Site in Zeolite for Cooperative Catalysis of Olefin Metathesis with Brønsted Acid Site". United States. doi:10.1021/jacs.8b03012.
@article{osti_1455312,
title = {Entrapped Single Tungstate Site in Zeolite for Cooperative Catalysis of Olefin Metathesis with Brønsted Acid Site},
author = {Zhao, Pu and Ye, Lin and Sun, Zhenyu and Lo, Benedict T. W. and Woodcock, Harry and Huang, Chen and Tang, Chiu and Kirkland, Angus I. and Mei, Donghai and Edman Tsang, Shik Chi},
abstractNote = {Industrial olefin metathesis catalysts generally suffer from low reaction rates and require harsh reaction conditions for moderate activities. This is due to their inability to prevent metathesis active sites (MAS) from aggregation and their intrinsic poor adsorption and activation of olefin molecules. Here, isolated tungstate species as single molecular MAS is immobilized inside zeolite pores by Bronsted acid sites (BAS) on the inner surface. It is demonstrated for the first time that unoccupied BAS in atomic proximity to MAS enhance olefin adsorption and greatly facilitate the formation of metallocycle intermediates in a stereospecific manner. Thus, effective cooperative catalysis takes place over the BAS-MAS pair. In consequence, for the cross-metathesis of ethene and trans-2-butene to propene, under the same mild reaction conditions, the propene production rate over WOx/USY is ca. 7,300 times that over the industrial WO3/SiO2 based catalyst. A propene yield up to 79% (80% selectivity) without observable deactivation was obtained over WOx/USY for a wide range of reaction conditions.},
doi = {10.1021/jacs.8b03012},
journal = {Journal of the American Chemical Society},
number = 21,
volume = 140,
place = {United States},
year = {Mon Apr 16 00:00:00 EDT 2018},
month = {Mon Apr 16 00:00:00 EDT 2018}
}