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.

doi:10.1002/ange.202107947

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

Journal Article · 05 September 2021 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202107947 · OSTI ID:1818782

Milaković, Lara ^[1]; Hintermeier, Peter H. ^[2]; Liu, Yue ^[1];

^[1];

^[2]

Department of Chemistry and Catalysis Research Center Technische Universität München Lichtenbergstraβe 4 85748 Garching Germany
Department of Chemistry and Catalysis Research Center Technische Universität München Lichtenbergstraβe 4 85748 Garching Germany, Institute for Integrated Catalysis Pacific Northwest National Laboratory 902 Battelle Boulevard Richland WA 99352 USA

Abstract 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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Sponsoring Organization:: USDOE

OSTI ID:: 1818782

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 47 Vol. 133; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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