期刊
NATURE COMMUNICATIONS
卷 8, 期 -, 页码 -出版社
NATURE PUBLISHING GROUP
DOI: 10.1038/ncomms14113
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资金
- U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences
- DOE's Office of Biological and Environmental Research located at Pacific Northwest National Laboratory (PNNL)
The dehydration of alcohols is involved in many organic conversions but has to overcome high free-energy barriers in water. Here we demonstrate that hydronium ions confined in the nanopores of zeolite HBEA catalyse aqueous phase dehydration of cyclohexanol at a rate significantly higher than hydronium ions in water. This rate enhancement is not related to a shift in mechanism; for both cases, the dehydration of cyclohexanol occurs via an E1 mechanism with the cleavage of C-beta-H bond being rate determining. The higher activity of hydronium ions in zeolites is caused by the enhanced association between the hydronium ion and the alcohol, as well as a higher intrinsic rate constant in the constrained environments compared with water. The higher rate constant is caused by a greater entropy of activation rather than a lower enthalpy of activation. These insights should allow us to understand and predict similar processes in confined spaces.
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