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Photocatalytic sacrificial H2 evolution dominated by micropore-confined exciton transfer in hydrogen-bonded organic frameworks

Nature Catalysis volume 6, pages 574–584 (2023)Cite this article

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Abstract

Organic semiconductors are attractive photocatalysts, but their quantum yields are limited by the transfer of photogenerated charges to the surface. A promising strategy for low-loss charge transfer is to shorten the distance from the bulk exciton coupling region to the catalyst surface. Here we employ the hydrogen-bonded organic framework 1,3,6,8-tetrakis(p-benzoic acid)pyrene (HOF-H4TBAPy) with hydrophilic one-dimensional micropore channels as a proof of concept for this approach. Under irradiation, photogenerated excitons rapidly transfer to the inner surface of adjacent micropores, engendering a mere 1.88 nm transfer route, thus significantly improving exciton utilization. When the micropore channel length does not exceed 0.59 μm, the sacrificial photocatalytic H2 evolution rate of HOF-H4TBAPy reaches 358 mmol h−1 g−1 and the apparent quantum yield at 420 nm is 28.6%. We further demonstrated a stable 1.03 mol day−1 m−2 H2 evolution on a 0.5 m2 HOF-H4TBAPy-loaded fibre under 1 Sun irradiation.

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Fig. 1: Structure of HOF-H4TBAPy.
Fig. 2: Probing exciton transfer confined within micropores using ultrafast spectroscopy.
Fig. 3: Tuning the accessibility of micropores to enhance the contribution of micropore-confined excitons.
Fig. 4: Identification of reaction sites in micropores.
Fig. 5: Photocatalytic H2 evolution performance of HOF-H4TBAPy.

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Data availability

The data that support the findings of this study are presented in the text and Supplementary Information. Additional data and information are available from the corresponding author on request. Source data are provided with this paper.

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Acknowledgements

This work was supported by the National Science Foundation of China (21872077), the National Key Research and Development Project of China (2020YFA0710304) and the Collaborative Innovation Center for Regional Environmental Quality. We thank Y. Weng, Z. Wang and Y. Xu (all IOP) for their support on the transient absorption spectroscopy tests. We are grateful to R. Zong, S. Yue and C. Ma (THU, Analysis Center) for their help with the electron microscopic analysis. We are also very grateful to E. Zhu (JLNU) for his useful suggestions in organic synthesis. Finally, we thank S. Yang, D. Wang (IMU) and Y. Guo (HNU) for their technical work in constructing outdoor photocatalytic systems.

Author information

Authors and Affiliations

  1. Department of Chemistry, Tsinghua University, Beijing, China

    Qixin Zhou, Yan Guo & Yongfa Zhu

  2. Department of Civil Engineering, The University of Hong Kong, Hong Kong, China

    Yan Guo

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  1. Qixin Zhou
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Contributions

Y.G., Y.Z. and Q.Z. co-proposed the idea and designed the experiments. Y.G. carried out the route design of organic synthesis and the sample synthesis. Y.G. and Q.Z. performed the ultrafast spectroscopic measurements and analysed the data. Y.G. performed the DFT calculations. Q.Z. carried out the crystal engineering design and physical modelling. Y.G and Q.Z. co-analysed the results. Y.G. and Y.Z. supervised the project. All the authors discussed the results and contributed to the writing of the paper.

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Correspondence to Yan Guo or Yongfa Zhu.

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Nature Catalysis thanks Robert Godin for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Methods, Figures 1–58, Notes 1–6, Tables 1–11 and References 1–78.

Supplementary Video 1

A plate reactor evolving and expelling H2 gas bubbles under an Xe lamp array (irradiation intensity: ~100 mW cm−2).

Supplementary Video 2

A plate reactor evolving and expelling H2 gas bubbles under natural sunlight (irradiation intensity: ~12.2 mW cm−2).

Supplementary Video 3

Nucleation of H2 bubbles on a non-woven fabric loaded with HOF under irradiation from a Xe lamp.

Supplementary Data 1

DFT atomic coordinates of the H4TBAPy molecule.

Supplementary Data 2

DFT atomic coordinates of a HOF crystal.

Source data

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Zhou, Q., Guo, Y. & Zhu, Y. Photocatalytic sacrificial H2 evolution dominated by micropore-confined exciton transfer in hydrogen-bonded organic frameworks. Nat Catal 6, 574–584 (2023). https://doi.org/10.1038/s41929-023-00972-x

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