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A semiconducting polymer bulk heterojunction photoanode for solar water oxidation


Organic semiconductors hold promise to enable scalable, low-cost and high-performance artificial photosynthesis. However, the performance of systems based on organic semiconductors for light-driven water oxidation have remained poor compared with inorganic semiconductors. Herein, we demonstrate an all-polymer bulk heterojunction organic semiconductor photoanode for solar water oxidation. By engineering the photoanode interlayers we gain important insights into critical factors (surface roughness and charge extraction efficiency) to increase the operational stability, which reaches above 3 h with a 1-Sun photocurrent density, Jph, of >3 mA cm−2 at 1.23 V versus the reversible hydrogen electrode for the sacrificial oxidation of Na2SO3 at pH 9. Optimizing the coupling to an oxygen evolution catalyst yields O2 production with Jph > 2 mA cm−2 at 1.23 V versus the reversible hydrogen electrode (100% Faradaic efficiency and a quantum efficiency up to 27% with 610 nm illumination), demonstrating improved stability (≥1 mA cm−2 for over 30 min of continuous operation) compared with previous organic photoanodes.

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Fig. 1: Components and device structure of the BHJ photoanode.
Fig. 2: ETL engineering of the BHJ photoanodes for stable sacrificial oxidation.
Fig. 3: Photoanode structure with HTL and OER catalyst for solar water oxidation.
Fig. 4: Quantum efficiency and O2 production.

Data Availability

Source data are provided with this paper. All data generated or analysed during this study are included in this published article and its Supplementary Information files, or are available from the authors upon reasonable request.


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We acknowledge support from the Swiss Competence Centre for Energy Research (SCCER Heat and Electricity Storage, contract number CTI 1155002545). N.G. and Y.L. thank the Swiss National Foundation (SNF) for funding under an Ambizione Energy Grant (PZENP2_166871). J.-H.Y. thanks a research agreement between EPFL and the Korea Electric Power Corporation (KEPCO).

Author information




K.S. and H.-H.C. conceived and designed the project. H.-H.C. prepared the photoanodes and measured the PEC performance. H.-H.C. and L.Y. performed the IPCE and GC measurements. H.-H.C. and J.-H.Y. prepared the ETLs and HTLs and performed the contact angle measurements. H.-H.C., Y.L. and R.A.W. performed the SEM and TEM measurements. Y.L. and F.B. analysed the impedance data. H.-H.C. and N.G. characterized the OER catalysts. H.-H.C. and A.S. synthesized the polymer donor and acceptor. K.S. and H.-H.C. prepared the manuscript and subsequent editing/improvement was performed by all authors.

Corresponding author

Correspondence to Kevin Sivula.

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Peer review information Nature Catalysis thanks Ludmilla Steier and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Methods, Discussions, Figs. 1–30, Tables 1 and 2 and References.

Supplementary Data 1

Source data for the chronoamperometric plots in Supplementary Figs. 3b, 4, 6b, 11b, 12d, 13b, 15b, 20b, 28b, 29b and 30b.

Source data

Source Data Fig. 2

Source data for the chronoamperometric plot.

Source Data Fig. 3

Source data for the chronoamperometric plot.

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Cho, HH., Yao, L., Yum, JH. et al. A semiconducting polymer bulk heterojunction photoanode for solar water oxidation. Nat Catal 4, 431–438 (2021).

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