Directing the Rate‐Enhancement for Hydronium Ion Catalyzed Dehydration via Organization of Alkanols in Nanoscopic Confinements

Shetty, Manish; Wang, Huamin; Chen, Feng; Jaegers, Nicholas; Liu, Yue; Camaioni, Donald M.; Gutiérrez, Oliver Y.; Lercher, Johannes A.

doi:10.1002/ange.202009835

Directing the Rate‐Enhancement for Hydronium Ion Catalyzed Dehydration via Organization of Alkanols in Nanoscopic Confinements

Journal Article · Fri Nov 27 00:00:00 EST 2020 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.202009835· OSTI ID:1724437

^[1]; ^[1]; Chen, Feng ^[1]; ^[1]; Liu, Yue ^[2]; ^[1]; ^[1]; ^[3]

Institute of Integrated Catalysis Pacific Northwest National Laboratory (PNNL) P.O. Box 999 Richland WA 99352 USA
Department of Chemistry and Catalysis Research Center Technical University München Lichtenbergstrasse 4 85747 München Germany
Institute of Integrated Catalysis Pacific Northwest National Laboratory (PNNL) P.O. Box 999 Richland WA 99352 USA, Department of Chemistry and Catalysis Research Center Technical University München Lichtenbergstrasse 4 85747 München Germany

Abstract

Alkanol dehydration rates catalyzed by hydronium ions are enhanced by the dimensions of steric confinements of zeolite pores as well as by intraporous intermolecular interactions with other alkanols. The higher rates with zeolite MFI having pores smaller than those of zeolite BEA for dehydration of secondary alkanols, 3‐heptanol and 2‐methyl‐3‐hexanol, is caused by the lower activation enthalpy in the tighter confinements of MFI that offsets a less positive activation entropy. The higher activity in BEA than in MFI for dehydration of a tertiary alkanol, 2‐methyl‐2‐hexanol, is primarily attributed to the reduction of the activation enthalpy by stabilizing intraporous interactions of the C _β ‐H transition state with surrounding alcohol molecules. Overall, we show that the positive impact of zeolite confinements results from the stabilization of transition state provided by the confinement and intermolecular interaction of alkanols with the transition state, which is impacted by both the size of confinements and the structure of alkanols in the E1 pathway of dehydration.

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Sponsoring Organization:: USDOE

OSTI ID:: 1724437

Alternate ID(s):: OSTI ID: 1786115

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 5 Vol. 133; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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Directing the Rate‐Enhancement for Hydronium Ion Catalyzed Dehydration via Organization of Alkanols in Nanoscopic Confinements

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