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Published January 5, 2024 | Published
Journal Article Open

Direct propylene epoxidation via water activation over Pd-Pt electrocatalysts

Abstract

Direct electrochemical propylene epoxidation by means of water-oxidation intermediates presents a sustainable alternative to existing routes that involve hazardous chlorine or peroxide reagents. We report an oxidized palladium-platinum alloy catalyst (PdPtO/C), which reaches a Faradaic efficiency of 66 ± 5% toward propylene epoxidation at 50 milliamperes per square centimeter at ambient temperature and pressure. Embedding platinum into the palladium oxide crystal structure stabilized oxidized platinum species, resulting in improved catalyst performance. The reaction kinetics suggest that epoxidation on PdPtO/C proceeds through electrophilic attack by metal-bound peroxo intermediates. This work demonstrates an effective strategy for selective electrochemical oxygen-atom transfer from water, without mediators, for diverse oxygenation reactions.

Copyright and License

© 2024 the authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original US government works. https://www.science.org/about/science-licenses-journal-article-reuse

Acknowledgement

We are grateful to S. Ehrlich, L. Ma, E. Stavitski, and D. Leshchev for their help in operating XAS experiments. We also appreciate A. Penn for taking high-resolution energy dispersive spectroscopy mapping of catalysts.

Funding

This research was supported by the US Department of Energy (DOE) Office of Science, Office of Basic Energy Sciences, Catalysis Science Program, award no. DE-SC0023207. K.M. gratefully acknowledges the support of the Sloan Foundation. This research used resources of the National Synchrotron Light Source II, a US DOE Office of Science User Facility operated by Brookhaven National Laboratory under contract no. DE-SC0012704.

Contributions

Conceptualization: M.C. and K.M. Methodology: M.C. Investigation: M.C., J.H.M., and J.S.A. Validation: M.C. and J.S.A. Visualization: M.C. Funding acquisition: K.M. Project administration: M.C. and K.M. Supervision: K.M. and Y.R.-L. Writing – original draft: M.C. Writing – review and editing: M.C., J.H.M., J.S.A., C.J., Y.R.-L., and K.M.

Data Availability

There are no restrictions on materials. All data needed to evaluate the conclusions in the paper are present in the paper or the supplementary materials. Tabular data underlying the figures are deposited in the Dryad data repository (34).

Conflict of Interest

M.C. and K.M. have filed a provisional patent application (no. 63/544,664) regarding the design of catalysts and electrodes.

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Additional details

Created:
January 9, 2024
Modified:
January 9, 2024