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Molecular Understanding of the Catalytic Consequence of Ketene Intermediates under Confinement

[Image: see text] Neutral ketene is a crucial intermediate during zeolite carbonylation reactions. In this work, the roles of ketene and its derivates (viz., acylium ion and surface acetyl) associated with direct C–C bond coupling during the carbonylation reaction have been theoretically investigate...

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Autores principales: Chen, Wei, Li, Guangchao, Yi, Xianfeng, Day, Sarah J., Tarach, Karolina A., Liu, Zhiqiang, Liu, Shang-Bin, Edman Tsang, Shik Chi, Góra-Marek, Kinga, Zheng, Anmin
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8461653/
https://www.ncbi.nlm.nih.gov/pubmed/34478267
http://dx.doi.org/10.1021/jacs.1c08036
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author Chen, Wei
Li, Guangchao
Yi, Xianfeng
Day, Sarah J.
Tarach, Karolina A.
Liu, Zhiqiang
Liu, Shang-Bin
Edman Tsang, Shik Chi
Góra-Marek, Kinga
Zheng, Anmin
author_facet Chen, Wei
Li, Guangchao
Yi, Xianfeng
Day, Sarah J.
Tarach, Karolina A.
Liu, Zhiqiang
Liu, Shang-Bin
Edman Tsang, Shik Chi
Góra-Marek, Kinga
Zheng, Anmin
author_sort Chen, Wei
collection PubMed
description [Image: see text] Neutral ketene is a crucial intermediate during zeolite carbonylation reactions. In this work, the roles of ketene and its derivates (viz., acylium ion and surface acetyl) associated with direct C–C bond coupling during the carbonylation reaction have been theoretically investigated under realistic reaction conditions and further validated by synchrotron radiation X-ray diffraction (SR-XRD) and Fourier transformed infrared (FT-IR) studies. It has been demonstrated that the zeolite confinement effect has significant influence on the formation, stability, and further transformation of ketene. Thus, the evolution and the role of reactive and inhibitive intermediates depend strongly on the framework structure and pore architecture of the zeolite catalysts. Inside side pockets of mordenite (MOR), rapid protonation of ketene occurs to form a metastable acylium ion exclusively, which is favorable toward methyl acetate (MA) and acetic acid (AcOH) formation. By contrast, in 12MR channels of MOR, a relatively longer lifetime was observed for ketene, which tends to accelerate deactivation of zeolite due to coke formation by the dimerization of ketene and further dissociation to diene and alkyne. Thus, we resolve, for the first time, a long-standing debate regarding the genuine role of ketene in zeolite catalysis. It is a paradigm to demonstrate the confinement effect on the formation, fate, and catalytic consequence of the active intermediates in zeolite catalysis.
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spelling pubmed-84616532021-09-24 Molecular Understanding of the Catalytic Consequence of Ketene Intermediates under Confinement Chen, Wei Li, Guangchao Yi, Xianfeng Day, Sarah J. Tarach, Karolina A. Liu, Zhiqiang Liu, Shang-Bin Edman Tsang, Shik Chi Góra-Marek, Kinga Zheng, Anmin J Am Chem Soc [Image: see text] Neutral ketene is a crucial intermediate during zeolite carbonylation reactions. In this work, the roles of ketene and its derivates (viz., acylium ion and surface acetyl) associated with direct C–C bond coupling during the carbonylation reaction have been theoretically investigated under realistic reaction conditions and further validated by synchrotron radiation X-ray diffraction (SR-XRD) and Fourier transformed infrared (FT-IR) studies. It has been demonstrated that the zeolite confinement effect has significant influence on the formation, stability, and further transformation of ketene. Thus, the evolution and the role of reactive and inhibitive intermediates depend strongly on the framework structure and pore architecture of the zeolite catalysts. Inside side pockets of mordenite (MOR), rapid protonation of ketene occurs to form a metastable acylium ion exclusively, which is favorable toward methyl acetate (MA) and acetic acid (AcOH) formation. By contrast, in 12MR channels of MOR, a relatively longer lifetime was observed for ketene, which tends to accelerate deactivation of zeolite due to coke formation by the dimerization of ketene and further dissociation to diene and alkyne. Thus, we resolve, for the first time, a long-standing debate regarding the genuine role of ketene in zeolite catalysis. It is a paradigm to demonstrate the confinement effect on the formation, fate, and catalytic consequence of the active intermediates in zeolite catalysis. American Chemical Society 2021-09-03 2021-09-22 /pmc/articles/PMC8461653/ /pubmed/34478267 http://dx.doi.org/10.1021/jacs.1c08036 Text en © 2021 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Chen, Wei
Li, Guangchao
Yi, Xianfeng
Day, Sarah J.
Tarach, Karolina A.
Liu, Zhiqiang
Liu, Shang-Bin
Edman Tsang, Shik Chi
Góra-Marek, Kinga
Zheng, Anmin
Molecular Understanding of the Catalytic Consequence of Ketene Intermediates under Confinement
title Molecular Understanding of the Catalytic Consequence of Ketene Intermediates under Confinement
title_full Molecular Understanding of the Catalytic Consequence of Ketene Intermediates under Confinement
title_fullStr Molecular Understanding of the Catalytic Consequence of Ketene Intermediates under Confinement
title_full_unstemmed Molecular Understanding of the Catalytic Consequence of Ketene Intermediates under Confinement
title_short Molecular Understanding of the Catalytic Consequence of Ketene Intermediates under Confinement
title_sort molecular understanding of the catalytic consequence of ketene intermediates under confinement
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8461653/
https://www.ncbi.nlm.nih.gov/pubmed/34478267
http://dx.doi.org/10.1021/jacs.1c08036
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