Cargando…
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...
Autores principales: | , , , , |
---|---|
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 |
_version_ | 1784748975179431936 |
---|---|
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. |
format | Online Article Text |
id | pubmed-9290721 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
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 |
work_keys_str_mv | AT milakoviclara influenceofintracrystallineionicstrengthinmfizeolitesonaqueousphasedehydrationofmethylcyclohexanols AT hintermeierpeterh influenceofintracrystallineionicstrengthinmfizeolitesonaqueousphasedehydrationofmethylcyclohexanols AT liuyue influenceofintracrystallineionicstrengthinmfizeolitesonaqueousphasedehydrationofmethylcyclohexanols AT baratheszter influenceofintracrystallineionicstrengthinmfizeolitesonaqueousphasedehydrationofmethylcyclohexanols AT lercherjohannesa influenceofintracrystallineionicstrengthinmfizeolitesonaqueousphasedehydrationofmethylcyclohexanols |