Tailoring nanoscopic confines to maximize catalytic activity of hydronium ions

Shi, Hui; Eckstein, Sebastian; Vjunov, Aleksei; Camaioni, Donald M.; Lercher, Johannes A.

doi:10.1038/ncomms15442

Tailoring nanoscopic confines to maximize catalytic activity of hydronium ions

Journal Article · Thu May 25 00:00:00 EDT 2017 · Nature Communications

DOI:https://doi.org/10.1038/ncomms15442· OSTI ID:1623891

^[1]; Eckstein, Sebastian ^[2]; Vjunov, Aleksei ^[3]; ^[3]; ^[4]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis; DOE/OSTI
Technische Univ. Munchen, Garching (Germany). Dept. of Chemistry and Catalysis Research Center
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis; Technische Univ. Munchen, Garching (Germany). Dept. of Chemistry and Catalysis Research Center

Acid catalysis by hydronium ions is ubiquitous in aqueous-phase organic reactions. Here we show that hydronium ion catalysis, exemplified by intramolecular dehydration of cyclohexanol, is markedly influenced by steric constraints, yielding turnover rates that increase by up to two orders of magnitude in tight confines relative to an aqueous solution of a Brønsted acid. The higher activities in zeolites BEA and FAU than in water are caused by more positive activation entropies that more than offset higher activation enthalpies. The higher activity in zeolite MFI with pores smaller than BEA and FAU is caused by a lower activation enthalpy in the tighter confines that more than offsets a less positive activation entropy. Molecularly sized pores significantly enhance the association between hydronium ions and alcohols in a steric environment resembling the constraints in pockets of enzymes stabilizing active sites.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1623891

Alternate ID(s):: OSTI ID: 1735943
OSTI ID: 1643787

Report Number(s):: PNNL-SA--121731; PII: BFncomms15442

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 8; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Tailoring nanoscopic confines to maximize catalytic activity of hydronium ions

Journal Article · Thu May 25 00:00:00 EDT 2017 · Nature Communications · OSTI ID:1643787

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
alcohol dehydration
biomass conversion
cyclohexanol
transition states
water
zeolite

Tailoring nanoscopic confines to maximize catalytic activity of hydronium ions

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References (48)

Cited By (3)

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