Differences in Mechanism and Rate of Zeolite-Catalyzed Cyclohexanol Dehydration in Apolar and Aqueous Phase

Chen, Feng; Shetty, Manish; Wang, Meng; Shi, Hui; Liu, Yuanshuai; Camaioni, Donald M.; Gutiérrez, Oliver Y.; Lercher, Johannes A.

doi:10.1021/acscatal.0c05674

Differences in Mechanism and Rate of Zeolite-Catalyzed Cyclohexanol Dehydration in Apolar and Aqueous Phase

Journal Article · Wed Feb 17 00:00:00 EST 2021 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.0c05674· OSTI ID:1781124

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

The rate of acid-base catalyzed dehydration of alcohols strongly depends on the solvent and the environment of the acid sites. In this work, we find that Brønsted acidic sites in large-pore zeolites, but not in medium-pore zeolites, catalyze cyclohexanol dehydration in decalin at significantly higher rates than hydrated hydronium ions in aqueous phase. Specifically, the difference in turnover rates between the two solvents amounts to two to three orders of magnitude on H-BEA and H-FAU, while being very modest (within a factor of 2) for H-MFI. Combining kinetic, isotopic tracer and 2H NMR measurements, it is established that cyclohexanol dehydration generally follows an E1-elimination pathway in decalin. A notable exception is the monomer dehydration route on H-MFI, which exhibits a much lower activation energy and a substantially negative activation entropy that appear to be associated with an E2-type mechanism. The C-O bond cleavage displays a dominant degree of rate control in decalin, which stands in contrast to deprotonation (C-H cleavage) being rate-limiting in aqueous-phase dehydration.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1781124

Report Number(s):: PNNL-SA--159842

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 5 Vol. 11; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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