Role of the ionic environment in enhancing the activity of reacting molecules in zeolite pores

Pfriem, Niklas; Hintermeier, Peter H.; Eckstein, Sebastian; Kim, Sungmin; Liu, Qiang; Shi, Hui; Milakovic, Lara; Liu, Yuanshuai; Haller, Gary L.; Baráth, Eszter; Liu, Yue; Lercher, Johannes A.

doi:10.1126/science.abh3418

Role of the ionic environment in enhancing the activity of reacting molecules in zeolite pores

Journal Article · Thu May 06 00:00:00 EDT 2021 · Science

DOI:https://doi.org/10.1126/science.abh3418· OSTI ID:1785054

^[1]; Hintermeier, Peter H. ^[1]; ^[1]; ^[2]; ^[3]; ^[4]; ^[1]; ^[5]; Haller, Gary L. ^[1]; ^[1]; ^[1]; ^[6]

Department of Chemistry and Catalysis Research Center, Technical University of Munich, Lichtenbergstrasse 4, 85747 Garching, Germany.
Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA 99352, USA.
Department of Chemistry and Catalysis Research Center, Technical University of Munich, Lichtenbergstrasse 4, 85747 Garching, Germany., Paul Scherrer Institute, Forschungsstrasse 111, 5232 Villigen PSI, Switzerland.
Department of Chemistry and Catalysis Research Center, Technical University of Munich, Lichtenbergstrasse 4, 85747 Garching, Germany., School of Chemistry and Chemical Engineering, Yangzhou University, Siwangting Road 180, 225009 Yangzhou, Jiangsu, China.
Department of Chemistry and Catalysis Research Center, Technical University of Munich, Lichtenbergstrasse 4, 85747 Garching, Germany., Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Songling Road 189, Laoshan District, Qingdao, China.
Department of Chemistry and Catalysis Research Center, Technical University of Munich, Lichtenbergstrasse 4, 85747 Garching, Germany., Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA 99352, USA.

Tailoring the molecular environment around catalytically active sites allows for the enhancement of catalytic reactivity through a hitherto unexplored pathway. In zeolites, the presence of water creates an ionic environment via the formation of hydrated hydronium ions and the negatively charged framework aluminum tetrahedra. The high density of cation-anion pairs determined by the aluminum concentration of a zeolite induces a high local ionic strength that increases the excess chemical potential of sorbed and uncharged organic reactants. Charged transition states (carbocations for example) are stabilized, which reduces the energy barrier and leads to higher reaction rates. Using the intramolecular dehydration of cyclohexanol on H-MFI zeolites in water, we quantitatively show an enhancement of the reaction rate by the presence of high ionic strength as well as show potential limitations of this strategy.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: FG02-01ER15183

OSTI ID:: 1785054

Alternate ID(s):: OSTI ID: 1811296

Journal Information:: Science, Journal Name: Science Journal Issue: 6545 Vol. 372; ISSN 0036-8075

Publisher:: American Association for the Advancement of Science (AAAS)Copyright Statement

Country of Publication:: United States

Language:: English

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