Molecular Tuning of Reactivity of Zeolite Protons in HZSM-5

Chen, Yaxin; Ma, Xinyou; Hack, John H.; Zhang, Shuhao; Peng, Anyang; Dombrowski, James P.; Voth, Gregory A.; Tokmakoff, Andrei; Kung, Mayfair C.; Kung, Harold H.

doi:10.1021/jacs.3c12680

Title: Molecular Tuning of Reactivity of Zeolite Protons in HZSM-5

Journal Article · 04 April 2024 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.3c12680 · OSTI ID:2480917

Chen, Yaxin ^[1]; Ma, Xinyou ^[2];

^[2]; Zhang, Shuhao ^[1];

^[1]; Dombrowski, James P. ^[1];

^[2];

^[2]; Kung, Mayfair C. ^[1];

^[1]

Northwestern University, Evanston, IL (United States)
University of Chicago, IL (United States)

In acidic HZSM-5 zeolite, the reactivity of a methanol molecule interacting with the zeolite proton is amenable to modification via coadsorbing a stochiometric amount of an electron density donor E to form the [(E)(CH₃OH)(HZ)] complex. The rate of the methanol in this complex undergoing dehydration to dimethyl ether was determined for a series of E with proton affinity (PA) ranging from 659 kJ mol^–1 for C₆F₆ to 825 kJ mol^–1 for C₄H₈O and was found to follow the expression: Ln(Rate) – Ln(Rate_N₂) = β(PA – PA_N₂)^γ, where E = N₂ is the reference and β and γ are constants. This trend is probably due to the increased stability of the solvated proton in the [(E)(CH₃OH)(HZ)] complex with increasing PA. Importantly, this is also observed in steady-state flow reactions when stoichiometric quantities of E are preadsorbed on the zeolite. As demonstrated with E being D₂O, the effect on methanol reactivity diminishes when E is present in excess of the [(E)(CH₃OH)(HZ)] complex. It is proposed that the methanol dehydration reaction involves [(E)(CH₃OH)(CH₃OH)(HZ)] as the transition state, which is supported by the isotopologue distribution of the initial dimethyl ether formed when a flow of CH₃OH was passed over ZSM-5 containing one CD₃OH per zeolite proton. Furthermore, the implication of this on the mechanism of catalytic methanol dehydration on HZSM-5 is discussed.

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Research Organization:: Northwestern University, Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-03ER15457

OSTI ID:: 2480917

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 15 Vol. 146; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Alcohols
Dehydration
Infrared light
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Title: Molecular Tuning of Reactivity of Zeolite Protons in HZSM-5

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