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Dynamic structural twist in metal–organic frameworks enhances solar overall water splitting

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Abstract

Photocatalytic overall water splitting holds great promise for solar-to-hydrogen conversion. Maintaining charge separation is a major challenge but is key to unlocking this potential. Here we discovered a metal–organic framework (MOF) that shows suppressed charge recombination. This MOF features electronically insulated Zn2+ nodes and two chemically equivalent, yet crystallographically independent, linkers. These linkers behave as an electron donor–acceptor pair with non-overlapping band edges. Upon photoexcitation, the MOF undergoes a dynamic excited-state structural twist, inducing orbital rearrangements that forbid radiative relaxation and thereby promote a long-lived charge-separated state. As a result, the MOF achieves visible-light photocatalytic overall water splitting, in the presence of co-catalysts, with an apparent quantum efficiency of 3.09 ± 0.32% at 365 nm and shows little activity loss in 100 h of consecutive runs. Furthermore, the dynamic excited-state structural twist is also successfully extended to other photocatalysts. This strategy for suppressing charge recombination will be applicable to diverse photochemical processes beyond overall water splitting.

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Fig. 1: Chemically segregated system construction and structural characterization.
Fig. 2: Analysis of orbitals and structures.
Fig. 3: Photocatalytic performance.
Fig. 4: Charge separation and proton migration performance.
Fig. 5: Performance comparison of CFA-Zn and CFA-Zn/Con.

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Data availability

Additional discussions and data supporting this article are available in the Supplementary Information. Source data are provided with this paper.

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Acknowledgements

This work was financially supported by the National Key Research and Development Program of China (2021YFA1500400 H.-L.J.), the NSFC (22331009 H.-L.J., U22A20401 H.-L.J., 22025304 J.J., 22033007 J.J., 22303091 Y.H.), the Strategic Priority Research Program of the CAS (XDB0450302 H.-L.J. and XDB0540000 H.-L.J.), the Innovation Program for Quantum Science and Technology (2021ZD0303303 J.J.), the CAS Project for Young Scientists in Basic Research (YSBR-005 J.J.), the International Partnership Program of CAS (123GJHZ2022028MI H.-L.J.), the China Postdoctoral Science Foundation (BX20230348 K.S., 2023M743374 K.S.) and the Xiaomi Young Scholars from Xiaomi Foundation. We thank J. Zhao for the use of the Hefei-NAMD code and G. Xu for the variable-temperature electrical measurements. This work was partially carried out at the Instruments Center for Physical Science, University of Science and Technology of China.

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Author notes

  1. These authors contributed equally: Kang Sun, Yan Huang.

Authors and Affiliations

  1. Hefei National Research Center for Physical Sciences at the Microscale, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, People’s Republic of China

    Kang Sun, Qingyu Wang, Yujie Zhou, Jingxue Wang, Qun Zhang, Yi Luo & Hai-Long Jiang

  2. Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei, People’s Republic of China

    Yan Huang & Jun Jiang

  3. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian National Laboratory for Clean Energy, Dalian, People’s Republic of China

    Fusai Sun & Fengtao Fan

  4. National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, People’s Republic of China

    Qingyu Wang & Xusheng Zheng

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Contributions

H.-L.J. conceived the idea, and supervised and directed the project. K.S. and J.W. performed the experiments. Y.H. and J.J. performed the theoretical calculations. F.S. and F.F. conducted the photon-irradiated Kelvin probe force microscopy experiments. Q.W. and X.Z. helped with the synchrotron XPS and sXAS measurements. Q.Z. and Y.Z. studied the femtosecond transient absorption spectra. Y.L. provided constructive discussions. H.-L.J. and K.S. analysed the data and co-wrote the paper. All authors discussed the results and commented on the paper.

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Correspondence to Jun Jiang or Hai-Long Jiang.

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Nature Chemistry thanks Sergio Navalon 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 Discussions 1–7, Figs. 1–86 and Tables 1–7.

Source data

Source Data Fig. 1

SEM image for MOF.

Source Data Fig. 2

Analysis of orbitals and structures.

Source Data Fig. 3

Photocatalytic performance.

Source Data Fig. 4

Charge separation and proton migration performance.

Source Data Fig. 5

Performance comparison of CFA-Zn and CFA-Zn/Con.

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Sun, K., Huang, Y., Sun, F. et al. Dynamic structural twist in metal–organic frameworks enhances solar overall water splitting. Nat. Chem. (2024). https://doi.org/10.1038/s41557-024-01599-6

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