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.

Advertisement

Nature Communications
  • View all journals
  • Search
  • My Account Login
  • Content Explore content
  • About the journal
  • Publish with us
  • Sign up for alerts
  • RSS feed
  1. nature
  2. nature communications
  3. articles
  4. article
Persistent semiquinone radicals enable efficient near-infrared-driven H2O2 photosynthesis
Download PDF
Download PDF
  • Article
  • Open access
  • Published: 02 March 2026

Persistent semiquinone radicals enable efficient near-infrared-driven H2O2 photosynthesis

  • Shuai Dou1,2 na1,
  • Yaning Zhang1,2 na1,
  • Jing Xu3,
  • Ying Zhang  ORCID: orcid.org/0000-0001-6394-32311,2,
  • Yang Lou  ORCID: orcid.org/0000-0002-8310-81501,2,
  • Jiawei Zhang1,2,
  • Yuming Dong  ORCID: orcid.org/0000-0002-2999-13251,2,
  • Yongfa Zhu  ORCID: orcid.org/0000-0001-8528-509X4 &
  • …
  • Chengsi Pan  ORCID: orcid.org/0000-0002-1624-42591,2 

Nature Communications , Article number:  (2026) Cite this article

  • 4553 Accesses

  • 2 Altmetric

  • Metrics details

We are providing an unedited version of this manuscript to give early access to its findings. Before final publication, the manuscript will undergo further editing. Please note there may be errors present which affect the content, and all legal disclaimers apply.

Subjects

  • Photocatalysis
  • Sustainability

Abstract

Photosynthesis of H2O2 under sunlight is a sustainable method; however, most developed photocatalysts utilize limited near-infrared light, which accounts for 52% of the solar spectrum. In typical near-infrared photocatalysts, excited electrons fall into low-energy sub-gap states, reducing the driving force for H2O2 generation. Here, a polydopamine-loaded porphyrin supramolecular photocatalyst efficiently utilizes near-infrared light for H2O2 production from H2O and O2, achieving an apparent quantum yield of 2.8% at 1020 nm. This substantial near-infrared utilization significantly boosts activity under full-spectrum irradiation, with an H2O2 generation rate of 3.37 mM/h and solar-to-chemical conversion efficiency of 2.2%. Persistent semiquinone radicals in polydopamine are demonstrated to enable ultrafast sub-gap electron transfer (ca. 79 fs) from porphyrin to polydopamine and facilitate near-infrared-driven •OOH radical generation, thereby accelerating H2O2 production. This study sheds light on the potential of near-infrared-responsive photocatalysts and offers insights into optimizing their performance for sustainable H2O2 synthesis.

Similar content being viewed by others

H2O2 generation from O2 and H2O on a near-infrared absorbing porphyrin supramolecular photocatalyst

Article 02 March 2023

Sustainable photocatalytic hydrogen peroxide production over octonary high-entropy oxide

Article Open access 03 November 2024

Ketyl radical-mediated exfoliation and electron storage for solar hydrogen peroxide production

Article Open access 12 December 2025

Data availability

The data that support the findings of this study are available within the main text and its Supplementary Information. Atomic coordinates of the optimized computational models of PDA/SA-TCPP are available in Supplementary Data 1. Source data are provided in this paper.

References

  1. Choi, J. et al. Photocatalytic Hydrogen peroxide production through functionalized semiconductive metal-organic frameworks. J. Am. Chem. Soc. 146, 11319–11327 (2024).

    Google Scholar 

  2. Hou, H., Zeng, X. & Zhang, X. Production of hydrogen peroxide by photocatalytic processes. Angew. Chem. Int. Ed. 59, 17356–17376 (2020).

    Google Scholar 

  3. Global hydrogen peroxide market forecast to experience a CAGR of 5.1% to 2030. Focus on Catalysts 2020, 3 (2020).

  4. Campos-Martin, J., Blanco-Brieva, G. & Fierro, J. Hydrogen peroxide synthesis: an outlook beyond the anthraquinone process. Angew. Chem. Int. Ed. 45, 6962–6984 (2006).

    Google Scholar 

  5. Teng, Z. et al. Atomically dispersed antimony on carbon nitride for the artificial photosynthesis of hydrogen peroxide. Nat. Catal. 4, 374–384 (2021).

    Google Scholar 

  6. Kou, M. et al. Molecularly engineered covalent organic frameworks for hydrogen peroxide photosynthesis. Angew. Chem. Int. Ed. 61, e202200413 (2022).

    Google Scholar 

  7. Yoshikawa, A. et al. Near-infrared light-driven H2O2 generation via metalloporphyrin-based covalent organic frameworks and nanodisks. ACS Appl. Energy Mater. 7, 9084–9088 (2024).

    Google Scholar 

  8. Ou, H. et al. Hydroxyl-bonded Co single atom site on boroncarbonitride surface realizes nonsacrificial H2O2 synthesis in the near-infrared region. Adv. Mater. 36, e2404851 (2024).

    Google Scholar 

  9. Zhang, Y. et al. H2O2 generation from O2 and H2O on a near-infrared absorbing porphyrin supramolecular photocatalyst. Nat. Energy 8, 361–371 (2023).

    Google Scholar 

  10. Qi, F. et al. Interfacial reaction-induced defect engineering: enhanced visible and near-infrared absorption of wide band gap metal oxides with abundant oxygen vacancies. ACS Appl. Mater. Interfaces 12, 55417–55425 (2020).

    Google Scholar 

  11. Zhang, T. et al. Constructing oxygen-related defects in carbon nanodots with Janus optical properties: noninvasive NIR fluorescent imaging and effective photocatalytic therapy. Adv. Mater. 35, e2302705 (2023).

    Google Scholar 

  12. Zhang, H. et al. Hydrogen radical mediated concerted electron−proton transfer in 1D sulfone-based covalent organic framework for boosting photosynthesis of H2O2. Angew. Chem. Int. Ed. 64, e2025166572025 (2025).

    Google Scholar 

  13. Shiraishi, Y. et al. Resorcinol-formaldehyde resins as metal-free semiconductor photocatalysts for solar-to-hydrogen peroxide energy conversion. Nat. Mater. 18, 985–993 (2019).

    Google Scholar 

  14. Rao, P. & Hayon, E. Experimental determination of the redox potential of the superoxide radical •O2−. Biochem. Biophys. Res. Commun. 51, 468–473 (1973).

    Google Scholar 

  15. Petlicki, J. & van de Ven, T. The equilibrium between the oxidation of hydrogen peroxide by oxygen and the dismutation of peroxyl or superoxide radicals in aqueous solutions in contact with oxygen. J. Chem. Soc. Faraday. Trans. 94, 2763–2767 (1998).

    Google Scholar 

  16. Andrés, C. et al. Superoxide anion chemistry—its role at the core of the innate immunity. Int. J. Mol. Sci. 24, 1841 (2023).

    Google Scholar 

  17. Liu, Y. et al. Dopamine-melanin colloidal nanospheres: an efficient near-infrared photothermal therapeutic agent for in vivo cancer therapy. Adv. Mater. 25, 1353–1359 (2013).

    Google Scholar 

  18. Zangmeister, R., Morris, T. & Tarlov, M. Characterization of polydopamine thin films deposited at short times by autoxidation of dopamine. Langmuir. 29, 8619–8628 (2013).

    Google Scholar 

  19. Deng, Y. et al. Reduction of superoxide radical intermediate by polydopamine for efficient hydrogen peroxide photosynthesis. Angew. Chem. Int. Ed. 63, e202319216 (2024).

    Google Scholar 

  20. Fei, B. et al. Coating carbon nanotubes by spontaneous oxidative polymerization of dopamine. Carbon 46, 1795–1797 (2008).

    Google Scholar 

  21. Panzella, L. et al. Atypical structural and pi-electron features of a melanin polymer that lead to superior free-radical-scavenging properties. Angew. Chem. Int. Ed. 52, 12684–12687 (2013).

    Google Scholar 

  22. Bailey, C. et al. Polydopamine as a visible-light photosensitiser for photoinitiated polymerisation. Angew. Chem. Int. Ed. 62, e202301678 (2023).

    Google Scholar 

  23. Song, Y. & Buettner, G. Thermodynamic and kinetic considerations for the reaction of semiquinone radicals to form superoxide and hydrogen peroxide. Free Radical Biol. Med. 49, 919–962 (2010).

    Google Scholar 

  24. Guo, Y. et al. Hydrogen atom transfer from HOO• to ortho-quinones explains the antioxidant activity of polydopamine. Angew. Chem. Int. Ed. 60, 15220–15224 (2021).

    Google Scholar 

  25. Liu, H. et al. Role of polydopamine’s redox-activity on its pro-oxidant, radical-scavenging, and antimicrobial activities. Acta Biomater. 88, 181–196 (2019).

    Google Scholar 

  26. Lee, D. et al. Sustainable hydrogen peroxide production based on dopamine through Janus-like mechanism transition from chemical to photocatalytic reactions. J. Catal. 411, 235–244 (2022).

    Google Scholar 

  27. Yaman, H., Baig, M. & Kayan, A. Synthesis and characterization of tetrasubstituted porphyrin Tin(IV) complexes and their adsorption properties over tetracycline antibiotics. Reactions 6, 12 (2025).

    Google Scholar 

  28. Kurochkin, I. et al. Vibrational spectra of 5,10,15,20-Tetraphenylporphyrin (H2TPP) and Platinum(II) 5,10,15,20-Tetra(phenyl/pentafluorophenyl)porphyrins (PtTPP and PtTF5PP). Macroheterocycles 14, 334–341 (2021).

    Google Scholar 

  29. Takei, K., Takahashi, R. & Noguchi, T. Correlation between the hydrogen-bond structures and the C═O stretching frequencies of carboxylic acids as studied by density functional theory calculations: theoretical basis for interpretation of infrared bands of carboxylic groups in proteins. J. Phys. Chem. B. 112, 6725–6731 (2008).

    Google Scholar 

  30. Vasilopoulou, M. et al. Porphyrin oriented self-assembled nanostructures for efficient exciton dissociation in high-performing organic photovoltaics. J. Mater. Chem. A. 2, 182–192 (2014).

    Google Scholar 

  31. Kasha, M., Rawls, H. & El-Bayoumi, M. The exciton model in molecular spectroscopy. Pure. Appl. Chem. 11, 371–392 (1965).

    Google Scholar 

  32. Wei, Z. et al. Artificial Photosynthesis of H2O2 through reversible photoredox transformation between catechol and o-benzoquinone on polydopamine-coated CdS. ACS Catal. 12, 11436–11443 (2022).

    Google Scholar 

  33. Jing, J. et al. Supramolecular Zinc porphyrin photocatalyst with strong reduction ability and robust built-in electric field for highly efficient hydrogen production. Adv. Energy Mater. 11, 2101392 (2021).

    Google Scholar 

  34. Pang, H. et al. Capacitance methodology for investigating defect states in energy gap of organic semiconductor. Org. Electron. 65, 275–299 (2019).

    Google Scholar 

  35. Lian, Z. et al. Near infrared light induced plasmonic hot hole transfer at a nano-heterointerface. Nat. Commun. 9, 2314 (2018).

    Google Scholar 

  36. Zheng, Y. et al. Heavily doped carbon nitride nanocrystal promotes visible-near-infrared photosynthesis of hydrogen peroxide with near-unit photon utilization. ACS Nano. 18, 14583–14594 (2024).

    Google Scholar 

  37. Xiao, Y. et al. Long-lived internal charge-separated state in two-dimensional metal-organic frameworks improving photocatalytic performance. ACS Energy Lett. 7, 2323–2330 (2022).

    Google Scholar 

  38. Liu, H. et al. Delocalized orbitals over metal clusters and organic linkers enable boosted charge transfer in metal-organic framework for overall CO2 photoreduction. Angew. Chem. Int. Ed. 63, e202411508 (2024).

    Google Scholar 

  39. Wolff, C. et al. All-in-one visible-light-driven water splitting by combining nanoparticulate and molecular co-catalysts on CdS nanorods. Nat. Energy 3, 862–869 (2018).

    Google Scholar 

  40. Miao, T. & Tang, J. Characterization of charge carrier behavior in photocatalysis using transient absorption spectroscopy. J. Chem. Phys. 152, 194201 (2020).

    Google Scholar 

  41. Sun, H. et al. Efficient photothermal persulfate activation for rapid removal of antibiotics by heat-promoted Co3+ to Co2+ conversion on Bi12CoO20 photocatalyst. J. Catal. 428, 115172 (2023).

    Google Scholar 

  42. Zhang, L. et al. Visible-light-driven non-oxidative dehydrogenation of alkanes at ambient conditions. Nat. Energy 7, 1042–1051 (2022).

    Google Scholar 

  43. Zhao, L. et al. H2O2 self-supplied CuFeOx nanosystem as fenton-like reaction agents for endogenous/exogenous responsive synergetic antibacterial therapy. Chem. Eng. J. 492, 152265 (2024).

    Google Scholar 

  44. Fan, Y., Liu, J. & Han, X. Important contributions of in-situ produced H2O2 during photocatalytic sterilization of air by self-doped Bi2.15WO6. Sep. Purif. Technol. 363, 132052 (2025).

    Google Scholar 

  45. H2O2, price, Sigma-Aldrich, https://www.sigmaaldrich.com/US/en/product/sial/18304, (accessed Jan 06, 2026).

  46. Ai, K. et al. Sp2 C-dominant N-doped carbon sub-micrometer spheres with a tunable size: a versatile platform for highly efficient oxygen-reduction catalysts. Adv. Mater. 25, 998–1003 (2013).

    Google Scholar 

  47. Dou, S. et al. Boosting photocatalytic oxygen reduction to hydrogen peroxide via chemisorbed oxygen activation on polydopamine-coated zinc oxide. J. Colloid Interface Sci. 691, 137370 (2025).

    Google Scholar 

  48. Pan, C. & Zhu, Y. New type of BiPO4 oxy-acid salt photocatalyst with high photocatalytic activity on degradation of dye. Environ. Sci. Technol. 44, 5570–5574 (2010).

    Google Scholar 

  49. Pan, C. et al. Efficient and stable H2O2 production from H2O and O2 on BiPO4 photocatalyst. Appl. Catal. B Environ. 316, 121675 (2022).

    Google Scholar 

  50. Sellers, R. Spectrophotometric determination of hydrogen peroxide using potassium titanium(IV) oxalate. Analyst 105, 950–954 (1990).

    Google Scholar 

  51. Liu, X. et al. Facile synthesis of biocompatible cysteine-coated CuS nanoparticles with high photothermal conversion efficiency for cancer therapy. Dalton. Trans. 43, 11709–11715 (2014).

    Google Scholar 

  52. Barros, M. C. F. et al. Diffusion of levodopa in aqueous solutions of hydrochloric acid at 25 °C. Chem. Thermodyn. 72, 44–47 (2014).

    Google Scholar 

  53. Wilke, C. & Chang, P. Correlation of diffusion coefficients in dilute solutions. AIChE Journal 1, 264 (1955).

    Google Scholar 

  54. Hines, A. & Maddo, R. Mass Transfer: Fundamentals and Applications (Prentice-Hall, 1985).

  55. Johnny, L. Development of a model to determine mass transfer coefficient and oxygen solubility in bioreactors. Heliyon. 3, e00248 (2017).

    Google Scholar 

  56. Hasan, M. et al. The influence of gas–liquid interfacial transport theory on numerical modelling of plasma activation of water. Plasma. Chem. Plasma. Process. 41, 1363 (2021).

    Google Scholar 

  57. Riet, K. Review of measuring methods and results in nonviscous gas-liquid mass transfer in stirred Vessels. Ind. Eng. Chem. Process Des. Dev. 18, 3 (1979).

    Google Scholar 

  58. Delley, B. From molecules to solids with the DMol3 approach. J. Chem. Phys. 113, 7756–7764 (2000).

    Google Scholar 

Download references

Acknowledgements

C. Pan acknowledged the National Natural Science Foundation of China (22476071, 22172065), the Natural Science Foundation of Hebei Province (E2024210028), and the Natural Science Foundation of Jiangsu Province (BK20201345).

Author information

Author notes
  1. These authors contributed equally: Shuai Dou, Yaning Zhang.

Authors and Affiliations

  1. School of Chemical and Material Engineering, Jiangnan University, Wuxi, Jiangsu, China

    Shuai Dou, Yaning Zhang, Ying Zhang, Yang Lou, Jiawei Zhang, Yuming Dong & Chengsi Pan

  2. International Joint Research Center for Photoresponsive Molecules and Materials, Jiangnan University, Wuxi, Jiangsu, China

    Shuai Dou, Yaning Zhang, Ying Zhang, Yang Lou, Jiawei Zhang, Yuming Dong & Chengsi Pan

  3. School of Food Science and Technology, Jiangnan University, Wuxi, Jiangsu, China

    Jing Xu

  4. Department of Chemistry, Tsinghua University, Beijing, China

    Yongfa Zhu

Authors
  1. Shuai Dou
    View author publications

    Search author on:PubMed Google Scholar

  2. Yaning Zhang
    View author publications

    Search author on:PubMed Google Scholar

  3. Jing Xu
    View author publications

    Search author on:PubMed Google Scholar

  4. Ying Zhang
    View author publications

    Search author on:PubMed Google Scholar

  5. Yang Lou
    View author publications

    Search author on:PubMed Google Scholar

  6. Jiawei Zhang
    View author publications

    Search author on:PubMed Google Scholar

  7. Yuming Dong
    View author publications

    Search author on:PubMed Google Scholar

  8. Yongfa Zhu
    View author publications

    Search author on:PubMed Google Scholar

  9. Chengsi Pan
    View author publications

    Search author on:PubMed Google Scholar

Contributions

S.D. conducted the experiments and performance evaluation. Y.N.Z. performed DFT calculations and analysis of the TAS data. J.X. and Y.Z. performed data analysis. J.Z., Y.D., and Y.L. participated in the paper discussions and interpretation of the results. Y.F.Z. supervised the project. C.P. wrote the manuscript with critical revision from all authors.

Corresponding author

Correspondence to Chengsi Pan.

Ethics declarations

Competing interests

The authors declare no competing financial interest.

Peer review

Peer review information

Nature Communications thanks Minsu Gu, Qingrui Zhang and the other anonymous reviewer(s) for their contribution to the peer review of this work. A peer review file is available.

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 )

Description of Additional Supplementary File (download PDF )

Supplementary Data 1 (download ZIP )

Transparent Peer Review file (download PDF )

Source data

Source Data (download XLSX )

Rights and permissions

Open Access This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License, which permits any non-commercial use, sharing, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if you modified the licensed material. You do not have permission under this licence to share adapted material derived from this article or parts of it. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by-nc-nd/4.0/.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Dou, S., Zhang, Y., Xu, J. et al. Persistent semiquinone radicals enable efficient near-infrared-driven H2O2 photosynthesis. Nat Commun (2026). https://doi.org/10.1038/s41467-026-70130-x

Download citation

  • Received: 09 September 2025

  • Accepted: 19 February 2026

  • Published: 02 March 2026

  • DOI: https://doi.org/10.1038/s41467-026-70130-x

Share this article

Anyone you share the following link with will be able to read this content:

Sorry, a shareable link is not currently available for this article.

Provided by the Springer Nature SharedIt content-sharing initiative

Download PDF

Advertisement

Explore content

  • Research articles
  • Reviews & Analysis
  • News & Comment
  • Videos
  • Collections
  • Subjects
  • Follow us on Facebook
  • Follow us on X
  • Sign up for alerts
  • RSS feed

About the journal

  • Aims & Scope
  • Editors
  • Journal Information
  • Open Access Fees and Funding
  • Calls for Papers
  • Editorial Values Statement
  • Journal Metrics
  • Editors' Highlights
  • Contact
  • Editorial policies
  • Top Articles

Publish with us

  • For authors
  • For Reviewers
  • Language editing services
  • Open access funding
  • Submit manuscript

Search

Advanced search

Quick links

  • Explore articles by subject
  • Find a job
  • Guide to authors
  • Editorial policies

Nature Communications (Nat Commun)

ISSN 2041-1723 (online)

nature.com footer links

About Nature Portfolio

  • About us
  • Press releases
  • Press office
  • Contact us

Discover content

  • Journals A-Z
  • Articles by subject
  • protocols.io
  • Nature Index

Publishing policies

  • Nature portfolio policies
  • Open access

Author & Researcher services

  • Reprints & permissions
  • Research data
  • Language editing
  • Scientific editing
  • Nature Masterclasses
  • Research Solutions

Libraries & institutions

  • Librarian service & tools
  • Librarian portal
  • Open research
  • Recommend to library

Advertising & partnerships

  • Advertising
  • Partnerships & Services
  • Media kits
  • Branded content

Professional development

  • Nature Awards
  • Nature Careers
  • Nature Conferences

Regional websites

  • Nature Africa
  • Nature China
  • Nature India
  • Nature Japan
  • Nature Middle East
  • Privacy Policy
  • Use of cookies
  • Legal notice
  • Accessibility statement
  • Terms & Conditions
  • Your US state privacy rights
Springer Nature

© 2026 Springer Nature Limited

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