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/anie.202107947

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

Journal Article · 06 September 2021 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.202107947 · OSTI ID:1818813

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.

View Journal Article

Cite

Export

Save

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1818813

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 47 Vol. 60; ISSN 1433-7851

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

Country of Publication:: Germany

Language:: English

References (28)

Protonenübertragung, Säure-Base-Katalyse und enzymatische Hydrolyse. Teil I: Elementarvorgänge Eigen, M. Angewandte Chemie, Vol. 75, Issue 12 https://doi.org/10.1002/ange.19630751202	journal	June 1963
Hydratstruktur und zwischenmolekulare Wechselwirkung in Polyelektrolyten Zundel, G. Angewandte Chemie, Vol. 81, Issue 14 https://doi.org/10.1002/ange.19690811402	journal	July 1969
Upgrading Pyrolysis Oil over Ni/HZSM-5 by Cascade Reactions Zhao, Chen; Lercher, Johannes A. Angewandte Chemie, Vol. 124, Issue 24 https://doi.org/10.1002/ange.201108306	journal	January 2012
Influence of Hydronium Ions in Zeolites on Sorption Eckstein, Sebastian; Hintermeier, Peter H.; Zhao, Ruixue Angewandte Chemie, Vol. 131, Issue 11 https://doi.org/10.1002/ange.201812184	journal	March 2019
Valence Isomerizations in Compounds with Strained Rings Vogel, E. Angewandte Chemie International Edition in English, Vol. 2, Issue 1 https://doi.org/10.1002/anie.196300011	journal	January 1963
Hydration Structure and Intermolecular Interaction in Polyelectrolytes Zundel, G. Angewandte Chemie International Edition in English, Vol. 8, Issue 7 https://doi.org/10.1002/anie.196904991	journal	July 1969
Upgrading Pyrolysis Oil over Ni/HZSM-5 by Cascade Reactions Zhao, Chen; Lercher, Johannes A. Angewandte Chemie International Edition, Vol. 51, Issue 24 https://doi.org/10.1002/anie.201108306	journal	January 2012
Influence of Hydronium Ions in Zeolites on Sorption Eckstein, Sebastian; Hintermeier, Peter H.; Zhao, Ruixue Angewandte Chemie International Edition, Vol. 58, Issue 11 https://doi.org/10.1002/anie.201812184	journal	March 2019
Beiträge zur Kenntniss der flüchtigen organischen Basen Hofmann, Aug. With. Annalen der Chemie und Pharmacie, Vol. 79, Issue 1 https://doi.org/10.1002/jlac.18510790103	journal	January 1851
Zur Kenntniss der Reihenfolge der Analgerung und Ausscheidung der Jodwasserstoffelemente in organischen Verbindungen Saytzeff, Alexander Justus Liebig's Annalen der Chemie, Vol. 179, Issue 3 https://doi.org/10.1002/jlac.18751790304	journal	January 1875
Investigation and Modeling of the Hydrothermal Stability of Technically Relevant Zeolites Lutz, W.; Toufar, H.; Kurzhals, R. Adsorption, Vol. 11, Issue 3-4 https://doi.org/10.1007/s10450-005-5406-9	journal	July 2005
Catalysis by Zeolites – Science and Technology Haag, W. O. Studies in Surface Science and Catalysis https://doi.org/10.1016/S0167-2991(08)63680-0	book	January 1994
Impact of the local environment of Brønsted acid sites in ZSM-5 on the catalytic activity in n-pentane cracking Schallmoser, S.; Ikuno, T.; Wagenhofer, M. F. Journal of Catalysis, Vol. 316 https://doi.org/10.1016/j.jcat.2014.05.004	journal	July 2014
Elementary steps and reaction pathways in the aqueous phase alkylation of phenol with ethanol Eckstein, Sebastian; Hintermeier, Peter H.; Olarte, Mariefel V. Journal of Catalysis, Vol. 352 https://doi.org/10.1016/j.jcat.2017.06.002	journal	August 2017
Towards understanding and predicting the hydronium ion catalyzed dehydration of cyclic-primary, secondary and tertiary alcohols Milakovic, Lara; Hintermeier, Peter H.; Liu, Qiang Journal of Catalysis, Vol. 390 https://doi.org/10.1016/j.jcat.2020.08.009	journal	October 2020
Impact of Aqueous Medium on Zeolite Framework Integrity Vjunov, Aleksei; Fulton, John L.; Camaioni, Donald M. Chemistry of Materials, Vol. 27, Issue 9 https://doi.org/10.1021/acs.chemmater.5b01238	journal	April 2015
Hydronium-Ion-Catalyzed Elimination Pathways of Substituted Cyclohexanols in Zeolite H-ZSM5 Hintermeier, Peter H.; Eckstein, Sebastian; Mei, Donghai ACS Catalysis, Vol. 7, Issue 11 https://doi.org/10.1021/acscatal.7b01582	journal	October 2017
The nature of adsorbed carbenium ions as active intermediates in catalysis by solid acids Kazanskii, V. B. Accounts of Chemical Research, Vol. 24, Issue 12 https://doi.org/10.1021/ar00012a004	journal	December 1991
Crystal structure and structure-related properties of ZSM-5 Olson, D. H.; Kokotailo, G. T.; Lawton, S. L. The Journal of Physical Chemistry, Vol. 85, Issue 15 https://doi.org/10.1021/j150615a020	journal	July 1981
Effects of Si/Al Ratio on the Distribution of Framework Al and on the Rates of Alkane Monomolecular Cracking and Dehydrogenation in H-MFI Janda, Amber; Bell, Alexis T. Journal of the American Chemical Society, Vol. 135, Issue 51 https://doi.org/10.1021/ja4081937	journal	December 2013
Catalytic Consequences of Spatial Constraints and Acid Site Location for Monomolecular Alkane Activation on Zeolites Gounder, Rajamani; Iglesia, Enrique Journal of the American Chemical Society, Vol. 131, Issue 5 https://doi.org/10.1021/ja808292c	journal	February 2009
Impact of Zeolite Aging in Hot Liquid Water on Activity for Acid-Catalyzed Dehydration of Alcohols Vjunov, Aleksei; Derewinski, Miroslaw A.; Fulton, John L. Journal of the American Chemical Society, Vol. 137, Issue 32 https://doi.org/10.1021/jacs.5b06169	journal	August 2015
Stability of Zeolites in Hot Liquid Water Ravenelle, Ryan M.; Schüβler, Florian; D’Amico, Andrew The Journal of Physical Chemistry C, Vol. 114, Issue 46 https://doi.org/10.1021/jp104639e	journal	November 2010
Structure of synthetic zeolite ZSM-5 Kokotailo, G. T.; Lawton, S. L.; Olson, D. H. Nature, Vol. 272, Issue 5652 https://doi.org/10.1038/272437a0	journal	March 1978
The active site of acidic aluminosilicate catalysts Haag, W. O.; Lago, R. M.; Weisz, P. B. Nature, Vol. 309, Issue 5969 https://doi.org/10.1038/309589a0	journal	June 1984
Enhancing the catalytic activity of hydronium ions through constrained environments Liu, Yuanshuai; Vjunov, Aleksei; Shi, Hui Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14113	journal	March 2017
Tailoring nanoscopic confines to maximize catalytic activity of hydronium ions Shi, Hui; Eckstein, Sebastian; Vjunov, Aleksei Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15442	journal	May 2017
Role of the ionic environment in enhancing the activity of reacting molecules in zeolite pores Pfriem, Niklas; Hintermeier, Peter H.; Eckstein, Sebastian Science, Vol. 372, Issue 6545 https://doi.org/10.1126/science.abh3418	journal	May 2021

Similar Records

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

Journal Article · 2021 · Angewandte Chemie · OSTI ID:1818782

Milaković, Lara; Hintermeier, Peter H.; Liu, Yue; +2 more

Back Cover: Influence of Intracrystalline Ionic Strength in MFI Zeolites on Aqueous Phase Dehydration of Methylcyclohexanols (Angew. Chem. Int. Ed. 47/2021)

Journal Article · 2021 · Angewandte Chemie (International Edition) · OSTI ID:1860256

Milaković, Lara; Hintermeier, Peter H.; Liu, Yue; +2 more

Towards understanding and predicting the hydronium ion catalyzed dehydration of cyclic-primary, secondary and tertiary alcohols

Journal Article · 2020 · Journal of Catalysis · OSTI ID:1668765

Milakovic, Lara; Hintermeier, Peter H.; Liu, Qiang; +4 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemistry
alcohol dehydration
cyclic alcohols
ionic strength
volcano
zeolites

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

Citation Formats

References (28)

Similar Records

Related Subjects