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Hydrated CO2-mediated redox chemistry for biophotoelectrocatalytic oxyfunctionalization of C–H bonds

Nature Synthesis (2026)Cite this article

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Abstract

Biophotoelectrocatalysis provides chemo-, regio- and stereoselective routes to chemicals by coupling redox biocatalysis with photoelectrocatalysis. This biomimetic strategy, however, is limited by unwanted photoelectrocatalysis side reactions and the high cost of redox mediators. Here we report a sustainable biosolar platform that uses bicarbonate (HCO3−), a hydrated form of CO2, as a redox mediator to drive oxyfunctionalization of inert C–H bonds. Using molybdenum-doped bismuth vanadate as a model photoelectrode, we accelerate two-electron H2O oxidation for in situ H2O2 production and mitigate enzyme-damaging OH· generation via HCO3− photoredox chemistry. Photoelectrochemical and spectroscopic analyses revealed that HCO3− directs the H2O oxidation pathway towards H2O2 through the formation of a peroxycarbonate intermediate at the photoanode surface. The integration of HCO3− mediation with H2O2-dependent unspecific peroxygenase achieves an exceptional turnover of various enantioselective C–H oxyfunctionalization reactions under ambient conditions. The HCO3−-mediated H2O2 photosynthetic system opens up opportunities for sustainable oxygenative biosynthesis.

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Fig. 1: Schematic illustration of bicarbonate-mediated photoelectrocatalytic H2O oxidation to H2O2 for enantioselective oxyfunctionalization reactions.
Fig. 2: Photoelectrochemical oxidation of H2O to H2O2 using bicarbonate mediator.
Fig. 3: Reaction mechanism of bicarbonate-mediated photoelectrochemical H2O2 production.
Fig. 4: Bicarbonate-mediated, PEC-coupled biocatalytic enantioselective oxyfunctionalization.

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The data supporting the findings of the study are available within the paper and its Supplementary Information.

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Acknowledgements

This work was supported by National Research Foundation of Korea (NRF) grants funded by the Ministry of Science and ICT (grant numbers RS-2023-00222078, RS-2024-00440681, RS-2024-00460425). F.H. acknowledges funding by the European Union (ERC, PeroxyZyme, number 101054658).

Author information

Author notes

  1. These authors contributed equally: Chang Hyun Kim, Chung Hyeon Lee, Minkyung Lee.

Authors and Affiliations

  1. Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, Republic of Korea

    Chang Hyun Kim, Chung Hyeon Lee, Minkyung Lee, DongHwan Oh & Chan Beum Park

  2. Department of Materials Science and Engineering, Research Institute of Advanced Materials, Seoul National University, Seoul, Republic of Korea

    Yeongtaek Hong, Hyeon-Min Yu & WooChul Jung

  3. Department of Biotechnology, Delft University of Technology, Delft, Netherlands

    Frank Hollmann

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Contributions

C.H.K., C.H.L. and M.L. conceived the project, designed the research, performed experiments, analysed data and wrote the paper. C.B.P. supervised the research. D.O., Y.H. and H.-M.Y. performed experiments and analysed data. C.H.K., C.H.L., M.L., W.J. and C.B.P. discussed the photoelectrocatalysis. F.H. supplied the UPO enzymes. C.H.K., C.H.L., M.L., F.H. and C.B.P. commented on the photoelectrochemical biocatalysis. F.H. and C.B.P. reviewed the paper.

Corresponding author

Correspondence to Chan Beum Park.

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Nature Synthesis thanks Carla Casadevall, Han Sen Soo and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor Thomas West, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information (download PDF )

Supplementary Methods, Tables 1–4 and Figs. 1–29.

Source data

Source Data Fig. 2 (download XLSX )

Raw data on linear sweep voltammetric curves (Fig. 2b), Nyquist plots (Fig. 2c), and H2O2 production (Fig. 2d).

Source Data Fig. 3 (download XLSX )

Raw data on in situ Raman (Fig. 3a) and electron paramagnetic resonance spectra (Fig. 3c).

Source Data Fig. 4 (download XLSX )

Raw data on time profiles of biophotoelectrocatalytic reactions (Fig. 4a), photoluminescence spectra (Fig. 4b), and control experiments on various substrates (Fig. 4d).

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Kim, C.H., Lee, C.H., Lee, M. et al. Hydrated CO2-mediated redox chemistry for biophotoelectrocatalytic oxyfunctionalization of C–H bonds. Nat. Synth (2026). https://doi.org/10.1038/s44160-026-00998-6

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