Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Electrifying industrial hydrogen peroxide production via soft interfacial molecular mediation

Nature Chemistry volume 17, pages 1883–1890 (2025)Cite this article

Subjects

Abstract

Hydrogen peroxide is manufactured industrially via the anthraquinone autoxidation process—a typical thermocatalytic non-aqueous method. Despite a high interest in using renewable electricity to drive such processes, electrifying non-aqueous syntheses remains a substantial challenge. Here we present a multi-phase electrochemical anthraquinone autoxidation process that leverages an aqueous–non-aqueous interfacial proton-coupled electron transfer method facilitated by heterogeneous molecular mediation. This design enables the reduction of aqueous anthraquinones with high efficiency at high current densities, using only carbon electrodes. The method operates with high selectivity through a quinhydrone intermediate and prevents the over-reduction of aromatics during thermocatalytic hydrogenation. This approach combines the benefits of aqueous electrochemistry with those of the traditional non-aqueous process to achieve high current density electrochemistry with rapid kinetics and mass transport, while avoiding unwanted electrolyte in the hydrogen peroxide product. This strategy bridges aqueous electrochemistry with non-aqueous chemistry and establishes a framework for the electrification and decentralization of other non-aqueous chemical processes.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on SpringerLink
  • Instant access to the full article PDF.

USD 39.95

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Electrifying non-aqueous synthesis with aqueous electrochemistry with H2O2 production as a demonstration.
Fig. 2: Kinetics and thermodynamics of ANIPCET.
Fig. 3: Performance of the e-AO process for H2O2 production.
Fig. 4: General e-AO process.

Similar content being viewed by others

Data availability

All data are available in the Article and Supplementary Information, and are available via figshare at https://doi.org/10.6084/m9.figshare.29817470 (ref. 43).

References

  1. Goor, G., Glenneberg, J., Jacobi, S., Dadabhoy, J. & Candido, E. Hydrogen peroxide. In Ullmann’s Encyclopedia of Industrial Chemistry 1–40 (Wiley, 2019).

  2. Wang, H.-X., Toh, W. L., Tang, B. Y. & Surendranath, Y. Metal surfaces catalyse polarization-dependent hydride transfer from H2. Nat. Catal. 6, 351–362 (2023).

    Google Scholar 

  3. Twilton, J. et al. Quinone-mediated hydrogen anode for non-aqueous reductive electrosynthesis. Nature 623, 71–76 (2023).

    CAS  PubMed  PubMed Central  Google Scholar 

  4. Minteer, S. D. & Baran, P. Electrifying synthesis: recent advances in the methods, materials, and techniques for organic electrosynthesis. Acc. Chem. Res. 53, 545–546 (2020).

    CAS  PubMed  Google Scholar 

  5. Kawamata, Y. & Baran, P. S. Electrosynthesis: sustainability is not enough. Joule 4, 701–704 (2020).

    Google Scholar 

  6. Yan, M., Kawamata, Y. & Baran, P. S. Synthetic organic electrochemistry: calling all engineers. Angew. Chem. Int. Ed. Engl. 57, 4149–4159 (2017).

    PubMed  PubMed Central  Google Scholar 

  7. Jing, Y. et al. In situ electrochemical recomposition of decomposed redox-active species in aqueous organic flow batteries. Nat. Chem. 14, 1103–1109 (2022).

    CAS  PubMed  Google Scholar 

  8. Huskinson, B. et al. A metal-free organic–inorganic aqueous flow battery. Nature 505, 195–198 (2014).

    CAS  PubMed  Google Scholar 

  9. Elgazzar, A. & Wang, H. Beyond molecular transformations in electrochemical porous solid electrolyte reactors. Nat. Chem. Eng. 2, 3–7 (2025).

    Google Scholar 

  10. Mendez, M. A. et al. Molecular electrocatalysis at soft interfaces. Phys. Chem. Chem. Phys. 12, 15163–15171 (2010).

    CAS  PubMed  Google Scholar 

  11. Marken, F. & Wadhawan, J. D. Multiphase methods in organic electrosynthesis. Acc. Chem. Res. 52, 3325–3338 (2019).

    CAS  PubMed  Google Scholar 

  12. Perry, S. C. et al. Electrochemical synthesis of hydrogen peroxide from water and oxygen. Nat. Rev. Chem. 3, 442–458 (2019).

    CAS  Google Scholar 

  13. Tang, J. et al. Selective hydrogen peroxide conversion tailored by surface, interface, and device engineering. Joule 5, 1432–1461 (2021).

    CAS  Google Scholar 

  14. Zhang, X., Xia, Y., Xia, C. & Wang, H. Insights into practical-scale electrochemical H2O2 synthesis. Trends Chem. 2, 942–953 (2020).

    Google Scholar 

  15. Yamanaka, I. & Murayama, T. Neutral H2O2 synthesis by electrolysis of water and O2. Angew. Chem. Int. Ed. Engl. 120, 1926–1928 (2008).

    Google Scholar 

  16. Huang, A. et al. Direct H2O2 synthesis, without H2 gas. J. Am. Chem. Soc. 144, 14548–14554 (2022).

    CAS  PubMed  Google Scholar 

  17. Xia, C., Xia, Y., Zhu, P., Fan, L. & Wang, H. Direct electrosynthesis of pure aqueous H2O2 solutions up to 20% by weight using a solid electrolyte. Science 366, 226–231 (2019).

    CAS  PubMed  Google Scholar 

  18. Xia, Y. et al. Highly active and selective oxygen reduction to H2O2 on boron-doped carbon for high production rates. Nat. Commun. 12, 4225 (2021).

    CAS  PubMed  PubMed Central  Google Scholar 

  19. Zhang, X. et al. Electrochemical oxygen reduction to hydrogen peroxide at practical rates in strong acidic media. Nat. Commun. 13, 2880 (2022).

    CAS  PubMed  PubMed Central  Google Scholar 

  20. Preger, Y. et al. Quinone-mediated electrochemical O2 reduction accessing high power density with an off-electrode Co-N/C catalyst. Joule 2, 2722–2731 (2018).

    CAS  Google Scholar 

  21. Murray, A. T., Voskian, S., Schreier, M., Hatton, T. A. & Surendranath, Y. Electrosynthesis of hydrogen peroxide by phase-transfer catalysis. Joule 3, 2942–2954 (2019).

    CAS  Google Scholar 

  22. Huissoud, A. & Tissot, P. Electrochemical reduction of 2-ethyl-9,10-anthraquinone (EAQ) and mediated formation of hydrogen peroxide in a two-phase medium part II: production of alkaline hydrogen peroxide by the intermediate electroreduction of EAQ in a flow-by porous electrode in two-phase liquid–liquid flow. J. Appl. Electrochem. 29, 17–25 (1999).

    CAS  Google Scholar 

  23. Fink, A. G. et al. Indirect H2O2 synthesis without H2. Nat. Commun. 15, 766 (2024).

    CAS  PubMed  PubMed Central  Google Scholar 

  24. Ji, Y. et al. A phosphonate functionalized quinone redox flow battery at near‐neutral pH with record capacity retention rate. Adv. Energy Mater. 9, 1900039 (2019).

    Google Scholar 

  25. Chanda, A. & Fokin, V. V. Organic synthesis “on water”. Chem. Rev. 109, 725–748 (2009).

    CAS  PubMed  PubMed Central  Google Scholar 

  26. Fajt, V., Kurc, L. & Červený, L. The effect of solvents on the rate of catalytic hydrogenation of 6‐ethyl‐1,2,3,4‐tetrahydroanthracene-9,10-dione. Int. J. Chem. Kinet. 40, 240–252 (2008).

    CAS  Google Scholar 

  27. Patil, A., Curtin, D. & Paul, I. Interconversion by hydrogen transfer of unsymmetrically substituted quinhydrones in the solid state. Crystal structure of the 1:2 complex of 2, 5-dimethylquinone with hydroquinone. J. Am. Chem. Soc. 106, 4010–4015 (1984).

    CAS  Google Scholar 

  28. Patil, A., Curtin, D. & Paul, I. Solid-state formation of quinhydrones from their components. Use of solid-solid reactions to prepare compounds not accessible from solution. J. Am. Chem. Soc. 106, 348–353 (1984).

    CAS  Google Scholar 

  29. Mercado, F. V., Fernández, R. A., Iglesias, R. A. & Dassie, S. A. Facilitated proton transfer reactions via water autoprotolysis across oil| water interfaces. Spectroelectrochemical analysis. Electrochim. Acta 299, 430–440 (2019).

    Google Scholar 

  30. Goulet, M. A. et al. Extending the lifetime of organic flow batteries via redox state management. J. Am. Chem. Soc. 141, 8014–8019 (2019).

    CAS  PubMed  Google Scholar 

  31. Shang, H., Zhou, H., Zhang, W. & Zhang, K. Regeneration of working solution in the hydrogen peroxide production process. Can. J. Chem. Eng. 89, 1296–1302 (2011).

    CAS  Google Scholar 

  32. Lu, S., Wang, L., Wang, Y. & Mi, Z. Kinetic model of gas‐liquid‐liquid reactive extraction for production of hydrogen peroxide. Chem. Eng. Technol. 34, 823–830 (2011).

    CAS  Google Scholar 

  33. Oener, S. Z., Foster, M. J. & Boettcher, S. W. Accelerating water dissociation in bipolar membranes and for electrocatalysis. Science 369, 1099–1103 (2020).

    CAS  PubMed  Google Scholar 

  34. Kerr, E. F. et al. High energy density aqueous flow battery utilizing extremely stable, branching-induced high-solubility anthraquinone near neutral pH. ACS Energy Lett. 8, 600–607 (2022).

    Google Scholar 

  35. Kurc, L., Páter, M. & Červený, L. Activity of basic catalysts in oxidation of 2-ethyl-5,6,7,8-tetrahydro-9,10-anthrahydroquinone. J. Mol. Catal. A 202, 327–332 (2003).

    CAS  Google Scholar 

  36. Osakai, T., Okamoto, M., Sugihara, T. & Nakatani, K. Bimolecular-reaction effect on the rate constant of electron transfer at the oil/water interface as studied by scanning electrochemical microscopy. J. Electroanal. Chem. 628, 27–34 (2009).

    CAS  Google Scholar 

  37. Cukier, R. I. & Nocera, D. G. Proton-coupled electron transfer. Annu. Rev. Phys. Chem. 49, 337–369 (1998).

    CAS  PubMed  Google Scholar 

  38. Xia, C. et al. Continuous production of pure liquid fuel solutions via electrocatalytic CO2 reduction using solid-electrolyte devices. Nat. Energy 4, 776–785 (2019).

    CAS  Google Scholar 

  39. Lewis, R. J. & Hutchings, G. J. Selective oxidation using in situ-generated hydrogen peroxide. Acc. Chem. Res. 57, 106–119 (2023).

    PubMed  PubMed Central  Google Scholar 

  40. Bazant, M. Z. Unified quantum theory of electrochemical kinetics by coupled ion–electron transfer. Faraday Discuss. 246, 60–124 (2023).

    CAS  PubMed  Google Scholar 

  41. Shang, H. et al. Scalable and selective gold recovery from end-of-life electronics. Nat. Chem. Eng. 1, 170–179 (2024).

    Google Scholar 

  42. Han, C. et al. Electrocatalytic hydrogenation of alkenes with Pd/carbon nanotubes at an oil–water interface. Nat. Catal. 5, 1110–1119 (2022).

    CAS  Google Scholar 

  43. Xi, D. et al. Electrifying industrial hydrogen peroxide production via soft interfacial molecular mediation. figshare https://doi.org/10.6084/m9.figshare.29817470.v2 (2025).

Download references

Acknowledgements

This research was supported by The Harvard Climate and Sustainability Translational Fund.

Author information

Author notes

  1. These authors contributed equally: Dawei Xi, Yuheng Wu.

Authors and Affiliations

  1. Harvard John A. Paulson School of Engineering and Applied Sciences, Cambridge, MA, USA

    Dawei Xi, Yuheng Wu, Zifei Yan & Michael J. Aziz

  2. Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, USA

    Yuli Li & Richard Y. Liu

Authors
  1. Dawei Xi
    View author publications

    Search author on:PubMed Google Scholar

  2. Yuheng Wu
    View author publications

    Search author on:PubMed Google Scholar

  3. Yuli Li
    View author publications

    Search author on:PubMed Google Scholar

  4. Zifei Yan
    View author publications

    Search author on:PubMed Google Scholar

  5. Richard Y. Liu
    View author publications

    Search author on:PubMed Google Scholar

  6. Michael J. Aziz
    View author publications

    Search author on:PubMed Google Scholar

Contributions

D.X. conceived the idea. D.X. and Y.W. designed and conducted hardware design, tests and electrochemical experiments. Z.Y. studied the hydrogenation and performance of non-aqueous anthraquinones using hydrogen gas. Y.L. did the DFT calculation. R.Y.L. supervised the reaction mechanism study. M.J.A. supervised the project. D.X., Y.W. and M.J.A. drafted the manuscript. All authors edited the manuscript.

Corresponding authors

Correspondence to Dawei Xi or Michael J. Aziz.

Ethics declarations

Competing interests

Harvard University has filed a patent application (PCT/US25/10441) based on this work with D.X., Y.W. and M.J.A. as inventors for ‘Electrochemically reducing an aqueous-soluble, non-aqueous-insoluble molecule in an aqueous electrochemical cell to provide ANIHAT to a molecule from which H2O2 is produced upon exposure to O2’. M.J.A. is co-founder of Adiabatic Materials, a startup company that has licensed this intellectual property from Harvard. The remaining authors declare no competing interests.

Peer review

Peer review information

Nature Chemistry thanks Joaquim Henrique Teles and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information (download PDF )

Supplementary Figs. 1–27, Tables 1–4 and Data 1.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Xi, D., Wu, Y., Li, Y. et al. Electrifying industrial hydrogen peroxide production via soft interfacial molecular mediation. Nat. Chem. 17, 1883–1890 (2025). https://doi.org/10.1038/s41557-025-01940-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Version of record:

  • Issue date:

  • DOI: https://doi.org/10.1038/s41557-025-01940-7

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing