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3D-printed hierarchical pillar array electrodes for high-performance semi-artificial photosynthesis

Nature Materials volume 21, pages 811–818 (2022)Cite this article

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Abstract

The rewiring of photosynthetic biomachineries to electrodes is a forward-looking semi-artificial route for sustainable bio-electricity and fuel generation. Currently, it is unclear how the electrode and biomaterial interface can be designed to meet the complex requirements for high biophotoelectrochemical performance. Here we developed an aerosol jet printing method for generating hierarchical electrode structures using indium tin oxide nanoparticles. We printed libraries of micropillar array electrodes varying in height and submicrometre surface features, and studied the energy/electron transfer processes across the bio-electrode interfaces. When wired to the cyanobacterium Synechocystis sp. PCC 6803, micropillar array electrodes with microbranches exhibited favourable biocatalyst loading, light utilization and electron flux output, ultimately almost doubling the photocurrent of state-of-the-art porous structures of the same height. When the micropillars’ heights were increased to 600 µm, milestone mediated photocurrent densities of 245 µA cm–2 (the closest thus far to theoretical predictions) and external quantum efficiencies of up to 29% could be reached. This study demonstrates how bio-energy from photosynthesis could be more efficiently harnessed in the future and provide new tools for three-dimensional electrode design.

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Fig. 1: Next-generation electrodes for biophotoelectrochemistry.
Fig. 2: Aerosol jet printing of micropillar array electrodes.
Fig. 3: Printed micropillar electrodes exhibit high light transmission and cell loading.
Fig. 4: The photoelectrochemical performance of the Synechocystis-loaded electrodes.
Fig. 5: Structure–activity relationship analysis.

Data availability

All data used in this paper are available via the Apollo repository (https://doi.org/10.17863/CAM.80096) or on GitHub (https://github.com/JLawrence96/MicropillarArrayElectrodes).

Code availability

All code used in this paper are available via the Apollo respository (https://doi.org/10.17863/CAM.80096) or on GitHub (https://github.com/JLawrence96/MicropillarArrayElectrodes).

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Acknowledgements

This work was supported by the Biotechnology and Biological Sciences Research Council (BB/M011194/1 to J.M.L., BB/R011923/1 to J.Z. and X.C.), the Cambridge Trust (L.T.W.) and the Isaac Newton Trust (SCHERTEL SNSF3 to L.S.). S.K.-N. is grateful for support from a European Research Council (ERC) Starting Grant (ERC-2014-STG-639526, NANOGEN). S.K.-N. and Q.J. acknowledge support from the EPSRC Centre of Advanced Materials for Integrated Energy Systems (CAM-IES) (grant EP/P007767/1). We thank H. Lloyd-Laney and E. Kitson for helpful discussions in statistical analysis. We thank N. Plumeré and H. Li for helpful discussions in electrochemistry. We thank P. J. Bártolo and F. Liu for helpful discussions in 3D bioprinting.

Author information

Authors and Affiliations

  1. Yusuf Hamied Department of Chemistry, University of Cambridge, Cambridge, UK

    Xiaolong Chen, Lukas Schertel, Silvia Vignolini & Jenny Z. Zhang

  2. Department of Biochemistry, University of Cambridge, Cambridge, UK

    Joshua M. Lawrence, Laura T. Wey & Christopher J. Howe

  3. Department of Materials Science and Metallurgy, University of Cambridge, Cambridge, UK

    Qingshen Jing & Sohini Kar-Narayan

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  1. Xiaolong Chen
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Contributions

J.Z.Z. and X.C. conceived the project and wrote the manuscript. X.C. was the lead experimenter, interpreted the data and produced Figs. 1–4. J.M.L. helped with the preparation of the manuscript, performed and interpreted the statistical analysis, and produced Fig. 5b. L.T.W. provided biological samples and expertise. L.S. helped to design and carry out and interpret the light transmission/reflection/absorption experiments. Q.J. helped to establish the initial protocol for aerosol jet printing pillars. S.V. helped guide the light experiments. C.J.H. contributed biological expertise and samples. S.K.-N. helped to guide the initial printing experiments. All contributed comments to the manuscript.

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Correspondence to Jenny Z. Zhang.

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Nature Materials thanks Lars Jeuken and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Notes 1–4, Figs. 1–16 and Tables 1–3.

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Chen, X., Lawrence, J.M., Wey, L.T. et al. 3D-printed hierarchical pillar array electrodes for high-performance semi-artificial photosynthesis. Nat. Mater. 21, 811–818 (2022). https://doi.org/10.1038/s41563-022-01205-5

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