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Direct electrochemical propylene epoxidation over amorphized perovskite oxide in non-halogenated aqueous electrolyte

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Abstract

Industrial routes for propylene oxide and propylene glycol production involve either explosive hydrogen peroxide or corrosive chlorine-containing reagents, which produce hazardous halogenated by-products. Direct aqueous electrooxidation is a safe and sustainable alternative that uses water as an oxygen source at a catalytically competent anode. Until now, the direct aqueous route has only been demonstrated on noble metals (Pd, Pt, Au, Ag), which are unstable unless operated in halogenated electrolytes. Here we have developed a noble metal- and halogen-free catalytic system using a cobalt-based perovskite oxide with a Faradaic efficiency of 40% toward propylene oxide and propylene glycol, maintained over 24 h of operation. Kinetic analysis revealed potential-dependent rate-limiting steps involving electrochemical oxygen species generation and thermochemical oxygen transfer to propylene. This work establishes a cost-effective and safe synthetic route with earth-abundant non-noble metal-based catalysts, not only for propylene epoxidation but also for other heterogeneous oxygen-transfer reactions.

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Fig. 1: Catalytic systems for epoxidation and their performances.
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Fig. 2: Catalytic surface evolution.
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Fig. 3: Parameter optimization.
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Fig. 4: Electrochemical kinetic studies.
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Fig. 5: Mechanistic investigation and stability.
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Data availability

The main data supporting the findings of this study are available within the article and related Supplementary Information. All other data are available from the authors upon request. Source data are provided with this paper.

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Acknowledgements

We acknowledge support from the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Catalysis Science Program (award no. DE-SC0023207). This work was funded in part by the Gordon and Betty Moore Foundation (through grant GBMF12889 to Caltech). We thank C. Seo, M. Chung, E. Cosner, T. N. Ton and B. Moss for insightful discussions.

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Authors and Affiliations

Authors

Contributions

K.K. designed the catalysts and electrolytes, performed all electrochemical measurements and catalyst characterizations, and wrote the initial draft of the paper. E.V.M. edited the paper. S.P.D.-K. reproduced measurements and edited the paper. C.J. helped with XPS data collection. J.S.A. helped with discussions regarding experiments and kinetic modelling. J.T.K., H.P. and Y.L. led and managed the TEM measurements. J.C.B. helped with flow reactor and transport modelling. P.H.O. assisted with EPR instrumentation. K.M. supervised the study, edited the paper, and supported the project.

Corresponding author

Correspondence to Karthish Manthiram.

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Nature Catalysis thanks Mengning Ding, Ung Lee and Zhongtao Li for their contribution to the peer review of this work.

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Koner, K., Adams, J.S., Miu, E.V. et al. Direct electrochemical propylene epoxidation over amorphized perovskite oxide in non-halogenated aqueous electrolyte. Nat Catal (2026). https://doi.org/10.1038/s41929-026-01535-6

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