Enhancing the catalytic activity of hydronium ions through constrained environments

Yuanshuai Liu, Aleksei Vjunov, Hui Shi, Sebastian Eckstein, Donald M. Camaioni, Donghai Mei, Eszter Baráth and Johannes A. Lercher ()
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Yuanshuai Liu: TU München
Aleksei Vjunov: Pacific Northwest National Laboratory, Institute for Integrated Catalysis
Hui Shi: Pacific Northwest National Laboratory, Institute for Integrated Catalysis
Sebastian Eckstein: TU München
Donald M. Camaioni: Pacific Northwest National Laboratory, Institute for Integrated Catalysis
Donghai Mei: Pacific Northwest National Laboratory, Institute for Integrated Catalysis
Eszter Baráth: TU München
Johannes A. Lercher: TU München

Nature Communications, 2017, vol. 8, issue 1, 1-8

Abstract: Abstract 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 Cβ–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.

Date: 2017
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DOI: 10.1038/ncomms14113

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