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Epoxidation of Cyclooctene Using Water as the Oxygen Atom Source at Manganese Oxide Electrocatalysts

Jin, Kyoungsuk and Maalouf, Joseph H. and Lazouski, Nikifar and Corbin, Nathan and Yang, Dengtao and Manthiram, Karthish (2019) Epoxidation of Cyclooctene Using Water as the Oxygen Atom Source at Manganese Oxide Electrocatalysts. Journal of the American Chemical Society, 141 (15). pp. 6413-6418. ISSN 0002-7863. doi:10.1021/jacs.9b02345. https://resolver.caltech.edu/CaltechAUTHORS:20220505-565298000

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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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.9b02345DOIArticle
ORCID:
AuthorORCID
Jin, Kyoungsuk0000-0003-3009-6691
Maalouf, Joseph H.0000-0003-0017-0387
Lazouski, Nikifar0000-0002-4655-2041
Corbin, Nathan0000-0001-6074-7948
Yang, Dengtao0000-0002-8315-5467
Manthiram, Karthish0000-0001-9260-3391
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.
Funders:
Funding AgencyGrant Number
Massachusetts Institute of Technology (MIT)UNSPECIFIED
NSF Graduate Research FellowshipDGE-1122374
Subject Keywords:Oxides, Organic reactions, Ethers, Hydrocarbons, Oxygen
Issue or Number:15
DOI:10.1021/jacs.9b02345
Record Number:CaltechAUTHORS:20220505-565298000
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20220505-565298000
Official Citation:Epoxidation of Cyclooctene Using Water as the Oxygen Atom Source at Manganese Oxide Electrocatalysts Kyoungsuk Jin, Joseph H. Maalouf, Nikifar Lazouski, Nathan Corbin, Dengtao Yang, and Karthish Manthiram Journal of the American Chemical Society 2019 141 (15), 6413-6418 DOI: 10.1021/jacs.9b02345
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:114620
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:06 May 2022 23:20
Last Modified:06 May 2022 23:20

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