Structure and Dynamics of Zr6O8 Metal-Organic Framework Node Surfaces Probed with Ethanol Dehydration as a Catalytic Test Reaction

Dong Yang, Manuel A. Ortuño, Varinia Bernales, Christopher J. Cramer, Laura Gagliardi, Bruce C. Gates

Research output: Contribution to journalArticlepeer-review

73 Scopus citations


Some metal-organic frameworks (MOFs) incorporate nodes that are metal oxide clusters such as Zr6O8. Vacancies on the node surfaces, accidental or by design, act as catalytic sites. Here, we report elucidation of the chemistry of Zr6O8 nodes in the MOFs UiO-66 and UiO-67 having used infrared and nuclear magnetic resonance spectroscopies to determine the ligands on the node surfaces originating from the solvents and modifiers used in the syntheses and having elucidated the catalytic properties of the nodes for ethanol dehydration, which takes place selectively to make diethyl ether but not ethylene at 473-523 K. Density functional theory calculations show that the key to the selective catalysis is the breaking of node-linker bonds (or the accidental adjacency of open/defect sites) that allows catalytically fruitful bonding of the reactant ethanol to neighboring sites on the nodes, facilitating the bimolecular ether formation through an SN2 mechanism.

Original languageEnglish (US)
Pages (from-to)3751-3759
Number of pages9
JournalJournal of the American Chemical Society
Issue number10
StatePublished - Mar 14 2018

Bibliographical note

Funding Information:
We thank Professors Omar K. Farha and Joseph T. Hupp of Northwestern University for valuable comments. This work was supported as part of the Inorganometallic Catalyst Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (DE-SC0012702). The authors acknowledge the Minnesota Supercomputing Institute (MSI) for providing resources that contributed to the results.

Publisher Copyright:
© 2018 American Chemical Society.

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