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Enhanced hydrogen peroxide photosynthesis in covalent organic frameworks through induced asymmetric electron distribution

Nature Synthesis volume 4, pages 134–141 (2025)Cite this article

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Abstract

Covalent organic frameworks (COFs) can be used as photocatalysts for the direct photosynthesis of hydrogen peroxide (H2O2) from oxygen, water and sunlight. However, their highly symmetric structure can lead to weak adsorption of O2 and, therefore, unsatisfactory photocatalytic performance. Here we explore the local asymmetric electron distribution induced by Pauli and electron–electron repulsion in COFs to construct localized bonding sites for O2 species, which promotes photocatalytic H2O2 production. Experimental results and theoretical calculations reveal that TAPT–FTPB COFs (where TAPT is 1,3,5-tris-(4-aminophenyl) triazine and FTPB is 5-(5-formylthiophen-2-yl)thiophene-2-carbaldehyde) with an asymmetric electron distribution show strong O2 adsorption interaction and a record-breaking solar-to-chemical conversion efficiency of 1.22% for direct photosynthesis of H2O2 from oxygen and water, which is higher than in the photosynthesis of plants (~0.1%). A flow-type photocatalytic microreactor integrated with TAPT–FTPB COFs exhibits 100% sterilization efficiency for killing bacteria and 97.8% conversion for photocatalytic 2-thiophene methylamine coupling. This work reports a strategy for manipulating the local electron distribution in COFs, opening the door for research on the rational design of high-performance photocatalysis with a local asymmetric electron distribution.

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Fig. 1: Molecular design of TAPT–FTPB COFs with local asymmetric electron distribution.
Fig. 2: Chemical bonding and structural characterization of TAPT–FTPB COFs.
Fig. 3: Photosynthesis of H2O2 over TAPT–FTPB COFs from H2O and O2.
Fig. 4: Photocatalytic mechanism for H2O2 synthesis.

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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 National Science Fund for Distinguished Young Scholars (no. 52025133), National Key R&D Program of China (no. 2022YFE0128500), National Natural Science Foundation of China (nos. 52025133, 52261135633, 52303363 and 52302207), China National Petroleum Corporation-Peking University Strategic Cooperation Project of Fundamental Research, the Beijing Natural Science Foundation (no. Z220020), New Cornerstone Science Foundation through the XPLORER PRIZE, CNPC Innovation Found (no. 2021DQ02-1002), China National Postdoctoral Program for Innovative Talents (no. BX20220009) and Project funded by China Postdoctoral Science Foundation (nos. 2022M720225 and 2023M730029). We acknowledge the assistance of Rongjuan Feng in data collection and analysis for in situ FT-IR spectra.

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Authors and Affiliations

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

    Youxing Liu, Lu Li, Zhiyuan Sang, Hao Tan, Na Ye, Chenglong Sun, Zongqiang Sun, Mingchuan Luo & Shaojun Guo

  2. Beijing Innovation Centre for Engineering Science and Advanced Technology, Peking University, Beijing, China

    Shaojun Guo

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Contributions

S.G. conceived the project. Y.L. designed and performed the experiments. Y.L. and L.L. performed the DFT calculation. Y.L. conducted data analyses with the help of L.L., Z. Sang, H.T., N.Y., C.S., Z. Sun and M.L. All the authors participated in discussions of the research.

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Correspondence to Shaojun Guo.

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Nature Synthesis thanks Liqun Ye 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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Supplementary Figs. 1–49 and Tables 1–3.

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Liu, Y., Li, L., Sang, Z. et al. Enhanced hydrogen peroxide photosynthesis in covalent organic frameworks through induced asymmetric electron distribution. Nat. Synth 4, 134–141 (2025). https://doi.org/10.1038/s44160-024-00644-z

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