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H2O2 generation from O2 and H2O on a near-infrared absorbing porphyrin supramolecular photocatalyst

Nature Energy volume 8, pages 361–371 (2023)Cite this article

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Abstract

Hydrogen peroxide (H2O2) is an important industrial chemical and also a possible energy carrier. Photocatalytic synthesis of H2O2 is an attractive alternative to the anthraquinone process, but current catalyst systems suffer from many problems including: a limited sunlight wavelength response, the need for sacrificial reagents and insufficient activity. Here we report self-assembled tetrakis(4-carboxyphenyl)porphyrin supramolecular photocatalysts that produce H2O2 from only H2O and O2 and with a quantum efficiency of 14.9% at 420 nm and 1.1% at 940 nm. The catalyst achieves a solar-to-chemical conversion efficiency of 1.2% at 328 K when irradiated and heated with simulated sunlight. Our results suggest that photogenerated electrons and holes contribute to H2O2 production by reacting on different active sites including pyrrole N–H ring and carboxyl groups. In particular, we propose a hole-induced H2O2 production process, which involves the photoconversion of -COOH to -CO3H groups on the catalyst, followed by thermal decomposition.

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Fig. 1: The characterization of crystalized SA-TCPP nanosheet.
Fig. 2: Band edge potentials of SA-TCPP supramolecular photocatalyst.
Fig. 3: The generation of the peroxy intermediate at 293 K the activity.
Fig. 4: H2O2 production performance on SA-TCPP supramolecular photocatalysts.
Fig. 5: Peroxy intermediates generation at 293 K and 353 K.

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The authors declare that all data supporting the findings of this study are available within the paper and Supplementary Information files. Source data are provided with this paper.

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Acknowledgements

C.P. acknowledges financial support from the National Natural Science Foundation of China (22172065) and Natural Science Foundation of Jiangsu Province (BK20201345). Ying Zhang and Y.D. acknowledge financial support from the Key Program of the National Natural Science Foundation of China (22136002). J.X. acknowledges financial support from the Natural Science Foundation of Jiangsu Province (BK20221541). Y.L. acknowledges financial support from the the National Key R&D Program of China (2021YFB3501900) and Natural Science Foundation of Jiangsu Province (BK20211239). Y. Zhu acknowledges financial support from the National Natural Science Foundation of China (21902009). We would also like to thank W. Wang from Shiyanjia Lab (www.shiyanjia.com) for the UPS analysis.

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Author notes

  1. These authors contributed equally: Yaning Zhang, Chengsi Pan.

Authors and Affiliations

  1. Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi, China

    Yaning Zhang, Chengsi Pan, Gaoming Bian, Yuming Dong, Ying Zhang & Yang Lou

  2. International Joint Research Center for Photoresponsive Molecules and Materials, Jiangnan University, Wuxi, China

    Yaning Zhang, Chengsi Pan, Gaoming Bian, Yuming Dong, Ying Zhang, Yang Lou & Yongfa Zhu

  3. School of Food Science and Technology, Jiangnan University, Wuxi, China

    Jing Xu

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

    Weixu Liu & Yongfa Zhu

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Contributions

C.P. conceived the idea. Yaning Zhang conducted performance evaluation and designed the isotopic experiments. G.B. and Ying Zhang conducted the fabrication experiments. J.X., Y.D., Y.L. and W.L. participated in the paper discussions. C.P. and Y. Zhu planned the research and wrote the paper. All the authors revised and approved the manuscript.

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Correspondence to Chengsi Pan or Yongfa Zhu.

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Zhang, Y., Pan, C., Bian, G. et al. H2O2 generation from O2 and H2O on a near-infrared absorbing porphyrin supramolecular photocatalyst. Nat Energy 8, 361–371 (2023). https://doi.org/10.1038/s41560-023-01218-7

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