Abstract
Hydrogen peroxide (H2O2) is not only a key eco-friendly oxidizer but also a promising energy carrier with an energy density comparable to that of compressed hydrogen. The industrial production of H2O2 relies on the energy-intensive and environmentally detrimental anthraquinone process, necessitating the exploration of greener alternatives. Here we demonstrate sustainable and unassisted electrochemical H2O2 production (via the two-electron oxygen reduction reaction) coupled to the oxidative valorization of glycerol, a biomass energy by-product, operating without external electric or solar energy inputs. We applied bismuth-loaded Pt and oxidized carbon nanotube electrocatalysts, for glycerol oxidation reaction and two-electron oxygen reduction reaction, respectively, which possess onset potentials close to the theoretical values for the electrochemical reactions. With this system, we achieved a high H2O2 production rate of approximately 8.475 μmol cm−2 min−1 and high glycerate selectivity for in situ glycerol oxidation reaction (74%), while producing renewable electricity on-site.

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Acknowledgements
This work was supported by the National Research Foundation of Korea for the grant by the South Korea Ministry of Science and ICT (MSIT) (grant nos. RS-2023-00222006, 2022H1D3A3A01081140 and RS-2024-00456139) (J.-W.J.), Basic Science Research Program (grant no. RS-2024-00451160), National Research Council of Science and Technology (NST) grant by the Korea government (MSIT) (grant no. GTL24011-102) (D.-H.S), US Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, and Catalysis Science Program to the SUNCAT Center for Interface Science and Catalysis, for ATR-FTIR studies, sample preparation, and TEM (T.F.J., S.-W.L.). The computational work was supported by the Supercomputing Center/Korea Institute of Science and Technology Information with supercomputing resources, including technical support (grant no. KSC-2024-CRE-0440). D.U.L., A.C., J.E.A.A. and J.E.M. acknowledge a cooperative research and development agreement sponsored by TotalEnergies American Services, Inc. (affiliate of TotalEnergies SE) under agreement number TC02307 for electrochemical cell development and DFT calculations. J.E.M. acknowledges a graduate fellowship through the National Science Foundation Graduate Research Fellowship under grant no. DGE-1656518. Y.X. acknowledges NSERC for their support in the form of a Banting postdoctoral fellowship.
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D.O., S.W.H., D.Y.K., J.E.M., T.F.J., D.-H.S. and J.-W.J. conceptualized this study. D.O., S.W.H., D.Y.K. and J.E.M. curated data. D.O., J.E.M., J.E.A.A., S.-W.L., Y.X. and D.U.L. established methodology. J.L. helped with HPLC measurements. A.C. helped with DFT calculations. T.F.J., D.-H.S. and J.-W.J. directed the research. D.O. visualized the data. D.O., S.W.H., D.Y.K., J.E.M., T.F.J., D.-H.S. and J.-W.J. cowrote the paper.
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Nature Synthesis thanks José Solla-Gullón, Kan Zhang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alexandra Groves, in collaboration with the Nature Synthesis team.
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Oh, D., Hwang, S.W., Kim, D.Y. et al. Unassisted electrochemical H2O2 production coupled to glycerol oxidation. Nat. Synth (2025). https://doi.org/10.1038/s44160-025-00774-y
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DOI: https://doi.org/10.1038/s44160-025-00774-y
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