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Photocatalysis of water into hydrogen peroxide over an atomic Ga-N5 site

Nature Synthesis volume 2, pages 557–563 (2023)Cite this article

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Abstract

Tuning photocatalytic selectivity towards industrially significant yet thermodynamically unfavourable products remains challenging. Here a Ga-N5 atomic site on macroporous inverse-opal-type carbon nitride (CNIO-GaSA) is designed and synthesized for visible-light-driven direct photosynthesis of hydrogen peroxide from molecular oxygen and water. The conversion of oxygen and water into hydrogen peroxide was found to occur via a metastable two-electron water oxidation and two-electron oxygen reduction pathway. The CNIO-GaSA photocatalyst exhibits a high reactivity of 331.7 μmol g−1 h−1 for H2O2 production, with a solar-to-chemical conversion efficiency of 0.4%, which is much higher than that for natural photosynthesis in plants (∼0.1%). Additionally, CNIO-GaSA installed in a photocatalytic flow system device can kill bacteria with 100% efficiency and retain high stability, indicating this system could be suitable for purifying natural water. Combined experimental characterizations and density functional theory simulations reveal that the intermediate states consisting of hybridized Ga 4p and N 2p from the Ga-N5 site can not only enhance the separation/transfer of charge carriers, but also promote the adsorption/activation of water and the formation of a *OH intermediate, which is the rate-determining step for two-electron water oxidation.

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Fig. 1: Structural characterization of CNIO-GaSA.
Fig. 2: Absorption, excitation properties and carrier mobility of CNIO-GaSA, CNIO and CN.
Fig. 3: Solar-driven H2O2 production and performance of a homemade continuous serial microreactor.
Fig. 4: Mechanism of photocatalytic H2O2 production over CNIO-GaSA and CN.

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Data availability

The data supporting the findings of this study are available within the article and its Supplementary Information.

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Acknowledgements

This study was financially supported by the National Key R&D Program of China (number 2022YFE0128500), the National Science Fund for Distinguished Young Scholars (number 52025133) and the Tencent Foundation through the XPLORER PRIZE.

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Author notes

  1. These authors contributed equally: Hao Tan, Peng Zhou.

Authors and Affiliations

  1. School of Materials Science and Engineering, Peking University, Beijing, P.R. China

    Hao Tan, Peng Zhou, Hongyu Guo, Yin Zhou, Yan Chen, Lingyou Zeng & Shaojun Guo

  2. State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, P.R. China

    Meixian Liu & Zhanfeng Zheng

  3. Institute of Physics, Chinese Academy of Sciences, Beijing, P.R. China

    Qinghua Zhang & Lin Gu

  4. College of Environmental Sciences and Engineering, Peking University, Beijing, P.R. China

    Fuyang Liu & Meiping Tong

  5. The Beijing Innovation Center for Engineering Science and Advanced Technology, Peking University, Beijing, P.R. China

    Shaojun Guo

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Contributions

S.G. conceived the idea and designed this study. H.T. synthesized the samples, conducted characterizations and performed photocatalytic reactions. P.Z. conducted the calculation study. M.L. performed the in situ FTIR tests. Q.Z and L.G. performed the HAADF-STEM imaging. F.L. performed the bactericidal experiments. H.G, Y.Z, Y.C., L.Z., Z.Z. and M.T provided suggestions on the manuscript. S.G., H.T. and P.Z. wrote the paper. All authors discussed the results and edited the paper.

Corresponding author

Correspondence to Shaojun Guo.

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Nature Synthesis thanks Shaohua Shen, Zhenyuan Teng, Hangxun Xu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary handling editor: Alexandra Groves, in collaboration with the Nature Synthesis team.

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Tan, H., Zhou, P., Liu, M. et al. Photocatalysis of water into hydrogen peroxide over an atomic Ga-N5 site. Nat. Synth 2, 557–563 (2023). https://doi.org/10.1038/s44160-023-00272-z

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