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Influence of Intracrystalline Ionic Strength in MFI Zeolites on Aqueous Phase Dehydration of Methylcyclohexanols

The impact of the concentration of hydrated hydronium ions and in turn of the local ionic strength in MFI zeolites has been investigated for the aqueous phase dehydration of 4‐methylcyclohexanol (E1 mechanism) and cis‐2‐methylcyclohexanol (E2 mechanism). The E2 pathway with the latter alcohol led to...

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Autores principales: Milaković, Lara, Hintermeier, Peter H., Liu, Yue, Baráth, Eszter, Lercher, Johannes A.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9290721/
https://www.ncbi.nlm.nih.gov/pubmed/34384139
http://dx.doi.org/10.1002/anie.202107947
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author Milaković, Lara
Hintermeier, Peter H.
Liu, Yue
Baráth, Eszter
Lercher, Johannes A.
author_facet Milaković, Lara
Hintermeier, Peter H.
Liu, Yue
Baráth, Eszter
Lercher, Johannes A.
author_sort Milaković, Lara
collection PubMed
description The impact of the concentration of hydrated hydronium ions and in turn of the local ionic strength in MFI zeolites has been investigated for the aqueous phase dehydration of 4‐methylcyclohexanol (E1 mechanism) and cis‐2‐methylcyclohexanol (E2 mechanism). The E2 pathway with the latter alcohol led to a 2.5‐fold higher activity. The catalytic activity normalized to the hydronium ions (turnover frequency, TOF) passed through a pronounced maximum, which is attributed to the increasing excess chemical potential of the alcohols in the pores, increasing in parallel with the ionic strength and the additional work caused by repulsive interactions and charge separation induced by the bulky alcohols. While the maximum in rate observed is invariant with the mechanism or substitution, the reaction pathway is influencing the activation parameters differently.
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spelling pubmed-92907212022-07-20 Influence of Intracrystalline Ionic Strength in MFI Zeolites on Aqueous Phase Dehydration of Methylcyclohexanols Milaković, Lara Hintermeier, Peter H. Liu, Yue Baráth, Eszter Lercher, Johannes A. Angew Chem Int Ed Engl Communications The impact of the concentration of hydrated hydronium ions and in turn of the local ionic strength in MFI zeolites has been investigated for the aqueous phase dehydration of 4‐methylcyclohexanol (E1 mechanism) and cis‐2‐methylcyclohexanol (E2 mechanism). The E2 pathway with the latter alcohol led to a 2.5‐fold higher activity. The catalytic activity normalized to the hydronium ions (turnover frequency, TOF) passed through a pronounced maximum, which is attributed to the increasing excess chemical potential of the alcohols in the pores, increasing in parallel with the ionic strength and the additional work caused by repulsive interactions and charge separation induced by the bulky alcohols. While the maximum in rate observed is invariant with the mechanism or substitution, the reaction pathway is influencing the activation parameters differently. John Wiley and Sons Inc. 2021-09-06 2021-11-15 /pmc/articles/PMC9290721/ /pubmed/34384139 http://dx.doi.org/10.1002/anie.202107947 Text en © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH https://creativecommons.org/licenses/by-nc-nd/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ (https://creativecommons.org/licenses/by-nc-nd/4.0/) License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.
spellingShingle Communications
Milaković, Lara
Hintermeier, Peter H.
Liu, Yue
Baráth, Eszter
Lercher, Johannes A.
Influence of Intracrystalline Ionic Strength in MFI Zeolites on Aqueous Phase Dehydration of Methylcyclohexanols
title Influence of Intracrystalline Ionic Strength in MFI Zeolites on Aqueous Phase Dehydration of Methylcyclohexanols
title_full Influence of Intracrystalline Ionic Strength in MFI Zeolites on Aqueous Phase Dehydration of Methylcyclohexanols
title_fullStr Influence of Intracrystalline Ionic Strength in MFI Zeolites on Aqueous Phase Dehydration of Methylcyclohexanols
title_full_unstemmed Influence of Intracrystalline Ionic Strength in MFI Zeolites on Aqueous Phase Dehydration of Methylcyclohexanols
title_short Influence of Intracrystalline Ionic Strength in MFI Zeolites on Aqueous Phase Dehydration of Methylcyclohexanols
title_sort influence of intracrystalline ionic strength in mfi zeolites on aqueous phase dehydration of methylcyclohexanols
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9290721/
https://www.ncbi.nlm.nih.gov/pubmed/34384139
http://dx.doi.org/10.1002/anie.202107947
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