Overall photocatalytic water splitting by an organolead iodide crystalline material

Abstract

Organolead halide perovskites, primarily regarded as a high-performance semiconducting component in photovoltaics, have excellent optical and charge-transport characteristics that are advantageous for photocatalysis. However, their moisture-sensitive nature largely hinders their application to water splitting. Here we report a semiconductive organolead iodide layered crystalline material ([Pb8I8(H2O)3]8+[O2C(CH2)4CO2]4) with a bandgap of ~2.74 eV that demonstrates a high robustness over a wide pH range as well as under aqueous boiling conditions. The Earth-abundant material maintains excellent optical characteristics similar to those of perovskites, and includes suitable band positions, excellent carrier diffusion lengths (up to 1.4 μm) and long carrier lifetimes (up to 1.2 μs). When illuminated by sunlight and combined with trace amounts of a Rh co-catalyst, the hybrid iodoplumbate steadily and efficiently produces stoichiometric amounts of hydrogen and oxygen in a recyclable manner. Our findings extend the excellent optoelectronic properties of organolead halide materials from photovoltaics to photocatalytic water splitting.

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Fig. 1: X-ray crystallographic views of TJU-16.
Fig. 2: Stability analysis of TJU-16.
Fig. 3: Photophysical properties of TJU-16.
Fig. 4: Overall water-splitting performance of TJU-16 and TJU-16-Rh.

Data availability

The data that support the findings of this study are available from the corresponding author upon reasonable request. X-ray crystal structure data (CCDC no. 1983043) is available in Supplementary Data 1. The atomic coordinates of the DFT calculation data for TJU-16 and the 2D perovskite hydrolysis process are available in Supplementary Data 2 and 3, respectively.

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Acknowledgements

This work was supported by grants from the National Natural Science Foundation of China (21971197, 51772217 and 21603165), the Shanghai Rising-Star Program (no. 20QA1409500), the Recruitment of Global Youth Experts by China, the Fundamental Research Funds for the Central Universities and the Science & Technology Commission of Shanghai Municipality (14DZ2261100 and 19DZ2271500).

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Contributions

X.S. and H.F. conceived the project design. X.S. synthesized TJU-16 and conducted the overall water-splitting reactions. X.S., C.P., J.Y., Y.J. and X.Z. carried out the characterization of TJU-16. G.W. and J.S. performed the theoretical calculations. H.F. supervised the research. X.S., G.W. and H.F. wrote and revised the paper. All the authors commented on the paper.

Corresponding author

Correspondence to Honghan Fei.

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Peer review information Nature Catalysis thanks the anonymous reviewers for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–26, Tables 1–6 and references.

Supplementary Data 1

Crystallographic Data of TJU-16.

Supplementary Data 2

Atomic coordinates of TJU-16 (IS, TS and FS) in DFT calculations.

Supplementary Data 3

Atomic coordinates of 2D perovskites (IS, TS and FS) in DFT calculations.

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Song, X., Wei, G., Sun, J. et al. Overall photocatalytic water splitting by an organolead iodide crystalline material. Nat Catal 3, 1027–1033 (2020). https://doi.org/10.1038/s41929-020-00543-4

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