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Photoelectrocatalytic biosynthesis fuelled by microplastics

Nature Synthesis volume 1, pages 776–786 (2022)Cite this article

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Abstract

Biocatalytic artificial photosynthesis integrates photocatalysis and redox biocatalysis to synthesize value-added chemicals using solar energy. However, this nature-inspired approach suffers from sluggish rates of reaction because of challenging water oxidation kinetics. Here we report photoelectrochemical biosynthetic reactions that use non-recyclable real-world poly(ethylene terephthalate) (PET) microplastics as an electron feedstock. A Zr-doped haematite photoanode extracts electrons from hydrolysed PET solutions obtained from post-consumer PET waste, such as drinks bottles, and transfers the electrons to the bioelectrocatalytic site. Carbon-based cathodes receive the electrons to activate redox enzymes (for example, unspecific peroxygenase, L-glutamate dehydrogenase and ene-reductase from the old yellow enzyme family) that drive various organic synthetic reactions. These reactions include oxyfunctionalization of C–H bonds, amination of C=O bonds and asymmetric hydrogenation of C=C bonds. These photoelectrocatalytic–biocatalytic hybrid reactions achieve total turnover numbers of 362,000 (unspecific peroxygenase), 144,000 (L-glutamate dehydrogenase) and 1,300 (old yellow enzyme). This work presents a photoelectrocatalytic approach for integrating environmental remediation and biocatalytic photosynthesis towards sustainable solar-to-chemical synthesis.

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Fig. 1: Schematic diagram of solar-powered photoelectrochemical biosynthetic reactions using non-recyclable real-world PET microplastics.
Fig. 2: Bioelectrocatalytic synthesis using CFP-based materials.
Fig. 3: PEC reformation of PET microplastics using Fe2O3-based photoanodes.
Fig. 4: BPEC synthesis using real-world microplastics.
Fig. 5: Substrate scope of BPEC reactions using real-world PET microplastics.
Fig. 6: Synthetic efficiencies of oxidoreductases in state-of-the-art BPEC systems.

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The data supporting the findings of the study are available in the paper and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

This work was supported by the National Research Foundation (NRF) via the Creative Research Initiative Center (grant no. NRF-2015R1A3A2066191 (J.K., J.J. and C.B.P.)) and the Global PhD Fellowship Program (grant no. NRF-2019H1A2A1075810 (J.K.)), Republic of Korea.

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Authors and Affiliations

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

    Jinhyun Kim, Jinha Jang & Chan Beum Park

  2. Department of Biotechnology, Delft University of Technology, Delft, The Netherlands

    Thomas Hilberath & Frank Hollmann

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  1. Jinhyun Kim
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Contributions

J.K. conceived and designed the research, performed (photo)electrocatalytic/bioelectrocatalytic/photobiocatalytic experiments, analysed the data and wrote the manuscript. C.B.P. supervised the research. J.K., J.J. and C.B.P. discussed the photoelectrocatalysis. T.H. and F.H. provided J.K. and C.B.P. with the OYE and UPO enzymes. J.K., T.H. and F.H. commented on the biocatalysis. All authors contributed to revising the manuscript.

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Correspondence to Chan Beum Park.

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Nature Synthesis thanks Hao Song and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary handling editor: Peter Seavill, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Supplementary Methods, Tables 1–10 and Figs. 1–25.

Source data

Source Data Fig. 2

Raw data on H2O2 production (Fig. 2b), hydroxylation rate (Fig. 2c), NADH formation (Fig. 2f), amination rate (Fig. 2g) and hydrogenation rate (Fig. 2h) and their statistical information (for example, mean, standard deviation and P values).

Source Data Fig. 3

Raw data on the production of formate and acetate by PEC reformation of microplastics and their corresponding statistical data (for example, mean, standard deviation and P values).

Source Data Fig. 4

Raw data on rates of photobiocatalytic reactions fuelled by microplastics and their statistical information (for example, mean, standard deviation and P values).

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Kim, J., Jang, J., Hilberath, T. et al. Photoelectrocatalytic biosynthesis fuelled by microplastics. Nat. Synth 1, 776–786 (2022). https://doi.org/10.1038/s44160-022-00153-x

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