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Metal–organic frameworks embedded in a liposome facilitate overall photocatalytic water splitting

Nature Chemistry volume 13, pages 358–366 (2021)Cite this article

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Abstract

Metal–organic frameworks (MOFs) have been studied extensively in the hydrogen evolution reaction (HER) and the water oxidation reaction (WOR) with sacrificial reagents, but overall photocatalytic water splitting using MOFs has remained challenging, principally because of the fast recombination of photo-generated electrons and holes. Here we have integrated HER- and WOR-MOF nanosheets into liposomal structures for separation of the generated charges. The HER-MOF nanosheets comprise light-harvesting Zn–porphyrin and catalytic Pt–porphyrin moieties, and are functionalized with hydrophobic groups to facilitate their incorporation into the hydrophobic lipid bilayer of the liposome. The WOR-MOF flakes consist of [Ru(2,2′-bipyridine)3]2+-based photosensitizers and Ir–bipyridine catalytic centres, and are localized in the hydrophilic interior of the liposome. This liposome–MOF assembly achieves overall photocatalytic water splitting with an apparent quantum yield of (1.5 ± 1)% as a result of ultrafast electron transport from the antennae (Zn–porphyrin and [Ru(2,2′-bipyridine)3]2+) to the reaction centres (Pt–porphyrin and Ir–bipyridine) in the MOFs and efficient charge separation in the lipid bilayers.

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Fig. 1: Structure of the LP–MOF for overall photocatalytic water splitting and the proposed ‘Z-scheme’ electron-transfer chain in the LP–MOF system.
Fig. 2: HER-MOF and WOR-MOF structures.
Fig. 3: Preparation and characterization of HER-MOF and WOR-MOF.
Fig. 4: Construction and confocal fluorescence microscopy images of LP–HER-WOR-MOF.
Fig. 5: Photocatalytic activity of LP–MOF hybrids.
Fig. 6: Transient absorption spectra of HER-MOF and WOR-MOF.
Fig. 7: The photocatalytic cycle and energy level diagram.

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Data availability

Source data are provided with this paper. All of the data that support the findings of this study, including catalytic measurements, material characterizations and spectroscopic data, are available within the paper and its Supplementary Information files. Further requests about the data can be directed to the corresponding author.

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Acknowledgements

We acknowledge funding support from the Ministry of Science and Technology of China (2016YFA0200702) and the National Natural Science Foundation of China (no. 21671162 and no. 21721001). We acknowledge R. Huang and S. Zhang, B. Xu, Q. Wang, D. Guo and Y. Jiang for experimental help.

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Authors and Affiliations

  1. Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, P.R. China

    Huihui Hu, Zhiye Wang, Lingyun Cao, Lingzhen Zeng, Cankun Zhang & Cheng Wang

  2. Department of Chemistry, The University of Chicago, Chicago, IL, USA

    Wenbin Lin

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Contributions

H.H. and C.W. conceived and designed this project. H.H. carried out the synthesis of the materials, characterized the materials and analysed the data. L.C. helped with the data analysis and structural determination. H.H. also performed the catalysis study. Z.W. and C.Z. performed the transient absorption experiments and data analysis. L.Z. performed elemental analysis. H.H., C.W. and W.L. wrote the manuscript. All the authors discussed the results and commented on the manuscript.

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Correspondence to Cheng Wang.

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Supplementary Information

Supplementary Figures 1–67, Tables 1–12, general experimental and chemicals, methods and refs. 1–21.

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AFM height measurement.

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Spectroscopic source data.

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Statistical source data.

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Spectroscopic source data.

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Hu, H., Wang, Z., Cao, L. et al. Metal–organic frameworks embedded in a liposome facilitate overall photocatalytic water splitting. Nat. Chem. 13, 358–366 (2021). https://doi.org/10.1038/s41557-020-00635-5

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