Confined Ionic Environments Tailoring the Reactivity of Molecules in the Micropores of BEA-Type Zeolite

Kim, Sungmin; Chen, Feng; Camaioni, Donald M.; Derewinski, Miroslaw A.; Gutiérrez, Oliver Y.; Liu, Yue; Lercher, Johannes A.

doi:10.1021/jacs.4c03405

Confined Ionic Environments Tailoring the Reactivity of Molecules in the Micropores of BEA-Type Zeolite

Journal Article · Tue Jun 18 00:00:00 EDT 2024 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.4c03405· OSTI ID:2375560

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Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Technische Univ. Munchen, Garching (Germany)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Technische Univ. Munchen, Garching (Germany)

In the presence of water, hydronium ions formed within the micropores of zeolite H-BEA significantly influence the sur-rounding environment and the reactivity of organic substrates. The positive charge of these ions, coupled with the zeolite's negatively charged framework, results in an ionic environment that causes strongly non-ideal solvation behavior of cyclohex-anol. This leads to a significantly higher excess chemical potential in the initial state and stabilizes at the same time the charged transition state in the dehydration of cyclohexanol. As a result, the free-energy barrier of the reaction is lowered, leading to a marked increase in reaction rates. Nonetheless, there is a limit to the reaction rate enhancement by hydronium ion concentration. Experiments conducted with low concentrations of reactants show that beyond an optimal concentration, the required spatial rearrangement between hydronium ions and cyclohexanols inhibits further increases in the reaction rate, leading to a peak in the intrinsic activity of hydronium ions. The quantification of excess chemical potential in both initial and transition states for zeolites HBEA, along with findings from HMFI, provides a basis to generalize and predict rates for hydronium-ion catalyzed dehydration reactions in Brønsted zeolites.

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

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

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 2375560

Alternate ID(s):: OSTI ID: 2471612
OSTI ID: 2476316

Report Number(s):: PNNL-SA--197914

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 26 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
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