Enhanced photocatalytic hydrogen evolution from organic semiconductor heterojunction nanoparticles

Abstract

Photocatalysts formed from a single organic semiconductor typically suffer from inefficient intrinsic charge generation, which leads to low photocatalytic activities. We demonstrate that incorporating a heterojunction between a donor polymer (PTB7-Th) and non-fullerene acceptor (EH-IDTBR) in organic nanoparticles (NPs) can result in hydrogen evolution photocatalysts with greatly enhanced photocatalytic activity. Control of the nanomorphology of these NPs was achieved by varying the stabilizing surfactant employed during NP fabrication, converting it from a core–shell structure to an intermixed donor/acceptor blend and increasing H2 evolution by an order of magnitude. The resulting photocatalysts display an unprecedentedly high H2 evolution rate of over 60,000 µmol h−1 g−1 under 350 to 800 nm illumination, and external quantum efficiencies over 6% in the region of maximum solar photon flux.

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Fig. 1: Materials and energy levels.
Fig. 2: H2 evolution from PTB7-Th/EH-IDTBR nanoparticles.
Fig. 3: Bright-field cryo-TEM images of nanoparticle photocatalysts showing differences in internal nanoparticle morphology.
Fig. 4: Small-angle neutron scattering.
Fig. 5: Cryo-TEM images of NPs after deposition of Pt cocatalyst and 20 h H2 evolution.
Fig. 6: External quantum efficiencies and performance comparison.

Data availability

The data shown in the plots, and that support the findings of this study, are available from the corresponding authors on reasonable request.

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Acknowledgements

The research reported in this publication was supported by funding from King Abdullah University of Science and Technology Office of Sponsored Research (OSR) under awards no. OSR-2018-CARF/CCF-3079 and no. OSR-2015-CRG4-2572. This work was supported by the nSoft consortium. Certain commercial products or company names are identified here to describe our study adequately. Such identification is not intended to imply recommendation or endorsement by the National Institute of Standards and Technology, nor is it intended to imply that the products or names identified are necessarily the best available for the purpose.

Author information

J.K. developed the idea, designed and performed experiments, developed analytical tools, analysed data and wrote the paper. M.B. developed the idea, and designed and performed experiments. H.C., T.M., C.T.H. and M.S. designed and performed experiments, and co-wrote manuscript. S.G.L. and W.Z. designed and performed experiments. L.Z. and L.Z. performed experiments. D.H.A. and R.S. imaged nanoparticles. A.W. assisted with manuscript preparation. J.T. assisted with deuteration study. F.L., D.M.D., J.R.D. and I.M. supervised the project.

Correspondence to Jan Kosco or Iain McCulloch.

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Supplementary Figs. 1–16 and Tables 1–3.

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Kosco, J., Bidwell, M., Cha, H. et al. Enhanced photocatalytic hydrogen evolution from organic semiconductor heterojunction nanoparticles. Nat. Mater. (2020). https://doi.org/10.1038/s41563-019-0591-1

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