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Carbonylation of Dimethyl Ether to Methyl Acetate over SSZ-13

Lusardi, Marcella and Chen, Thomas T. and Kale, Matthew and Kang, Jong Hun and Neurock, Matthew and Davis, Mark E. (2020) Carbonylation of Dimethyl Ether to Methyl Acetate over SSZ-13. ACS Catalysis, 10 (1). pp. 842-851. ISSN 2155-5435. doi:10.1021/acscatal.9b04307.

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The small-pore zeolite with the chabazite framework topology, SSZ-13, is found to be an active catalyst in the carbonylation of dimethyl ether to methyl acetate (MA). The production of MA over SSZ-13 after 24 h on stream at 165 °C and 1 bar approaches that obtained from mordenite and is significantly higher than from ferrierite at comparable Si/Al of ca. 10. To understand the origin of the activity, SSZ-13 materials are synthesized with variable Si/Al, characterized via several techniques including multinuclear magic-angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, and evaluated for their carbonylation activity. While MA production rates increase with decreasing Si/Al, the correlation is nonlinear due to the effect of Si/Al on the acid site distribution within different confining environments, and the associated impact of the latter on the rate-determining transition state barrier. Enhanced MA production rates trend with acid sites located at the eight-membered ring (8MR) that are increasingly populated as framework Al content increases. Density functional theory analyses of transition state energies as a function of active site location support the experimental findings, where the lowest apparent barriers are associated with the methoxy groups that orient within the plane of the 8MR window. This is due to an optimal charge stabilization of the cationic transition states with the negatively charged oxygens within the 8MR window. The effects of catalyst chemical composition, separate from framework topology, are also investigated using SAPO-34 (the silicoaluminophosphate analog of SSZ-13). Analyses of the ¹H MAS NMR signals and carbonylation activity suggest that the higher acid site strength of SSZ-13 compared to that of the SAPO material is required for effective Brønsted acid catalysis of Koch-type carbonylation pathways.

Item Type:Article
Related URLs:
URLURL TypeDescription
Lusardi, Marcella0000-0002-7002-4257
Kale, Matthew0000-0002-3039-3111
Kang, Jong Hun0000-0002-4197-9070
Davis, Mark E.0000-0001-8294-1477
Additional Information:© 2019 American Chemical Society. Received: October 6, 2019; Revised: December 3, 2019; Published: December 6, 2019. The authors gratefully acknowledge Dr. Sonjong Hwang and Dr. Stacey Zones for their helpful insight on the synthesis and characterization of the materials used in this investigation. The authors also acknowledge the computing resources provided by the Minnesota Supercomputing Institute (MSI) at the University of Minnesota that contributed to the calculations reported in this study. Author Contributions: The manuscript was written through contributions of all the authors. All the authors have given approval to the final version of the manuscript. The authors thank Chevron for supporting the experimental work and the University of Minnesota for the computational efforts. The authors declare no competing financial interest.
Funding AgencyGrant Number
Chevron CorporationUNSPECIFIED
University of MinnesotaUNSPECIFIED
Subject Keywords:chabazite, carbonylation, acetic acid, confinement, small-pore zeolite
Issue or Number:1
Record Number:CaltechAUTHORS:20191209-081001667
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Official Citation:Carbonylation of Dimethyl Ether to Methyl Acetate over SSZ-13. Marcella Lusardi, Thomas T. Chen, Matthew Kale, Jong Hun Kang, Matt Neurock, and Mark E. Davis. ACS Catalysis 2020 10 (1), 842-851. DOI: 10.1021/acscatal.9b04307
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:100229
Deposited By: Tony Diaz
Deposited On:09 Dec 2019 18:12
Last Modified:16 Nov 2021 17:52

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