Epoxidation of Cyclooctene Using Water as the Oxygen Atom Source at Manganese Oxide Electrocatalysts
Abstract
Epoxides are useful intermediates for the manufacture of a diverse set of chemical products. Current routes of olefin epoxidation either involve hazardous reagents or generate stoichiometric side products, leading to challenges in separation and significant waste streams. Here, we demonstrate a sustainable and safe route to epoxidize olefin substrates using water as the oxygen atom source at room temperature and ambient pressure. Manganese oxide nanoparticles (NPs) are shown to catalyze cyclooctene epoxidation with Faradaic efficiencies above 30%. Isotopic studies and detailed product analysis reveal an overall reaction in which water and cyclooctene are converted to cyclooctene oxide and hydrogen. Electrokinetic studies provide insights into the mechanism of olefin epoxidation, including an approximate first-order dependence on the substrate and water and a rate-determining step which involves the first electron transfer. We demonstrate that this new route can also achieve a cyclooctene conversion of ∼50% over 4 h.
Additional Information
© 2019 American Chemical Society. Received 2 March 2019. Published online 9 April 2019. Published in issue 17 April 2019. We gratefully acknowledge Kindle Williams for insightful discussions and experimental assistance. We also thank the MIT Department of Chemistry Instrumentation Facility (DCIF) for the use of their NMR spectrometer. Funding for this research was provided by the Department of Chemical Engineering at MIT. J.H.M., N.L., and N.C. were supported by National Science Foundation Graduate Research Fellowships under Grant 1122374. The authors declare no competing financial interest.Attached Files
Supplemental Material - ja9b02345_si_001.pdf
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Additional details
- Eprint ID
- 114620
- Resolver ID
- CaltechAUTHORS:20220505-565298000
- Massachusetts Institute of Technology (MIT)
- DGE-1122374
- NSF Graduate Research Fellowship
- Created
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2022-05-06Created from EPrint's datestamp field
- Updated
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2022-05-06Created from EPrint's last_modified field