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Hierarchical assembly of donor–acceptor covalent organic frameworks for photosynthesis of hydrogen peroxide from water and air

Nature Synthesis (2024)Cite this article

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Abstract

Covalent organic frameworks (COFs) with ordered π skeletons and aligned nanopores could be ideal photocatalytic materials but remain unexplored for this use. Here we report hexavalent photocatalytic COFs for efficient photosynthesis via systematic design of the π skeletons and pores. The framework of the photocatalysts have donor-alt-acceptor arrangements and upon irradiation are converted into catalytic scaffolds, which have dense catalytic sites for oxygen reduction and water oxidation and spatially segregated donor and acceptor columns for hole and electron separation to prevent charge recombination and enable rapid charge transport. The pore walls are engineered to be hydrophilic to enable water and dissolved oxygen to pass through the one-dimensional channel to reach the catalytic sites via capillary effect. The COFs act as a photocatalyst for the photosynthesis of H2O2 using only water, air and light, attaining a high production rate of 7.2 mmol g–1 h–1, optimal apparent quantum yield of 18.0% and solar-to-chemical conversion efficiency of 0.91% in bath reactors. Flow reactors incorporating these COFs can continuously produce pure H2O2 solution, yielding over 15 litres under ambient conditions, and exhibit exceptional operational stability over 2 weeks of use.

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Fig. 1: Design of photocatalytic COFs for H2O2 manufacturing.
Fig. 2: Two-dimensional donor-alt-acceptor skeletons and stacking structures.
Fig. 3: Chemical and crystal structures.
Fig. 4: Photophysical and electrochemical properties.
Fig. 5: Hydrogen bonds and frontier orbitals.
Fig. 6: Tailor-made 1D channels and vapour sorption.
Fig. 7: Photocatalysis and active sites.
Fig. 8: In situ study.

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Data availability

Source Data are provided with this paper. All other data supporting the finding of this study are available within this article and its Supplementary Information. The atomic coordinates for the final optimized structures are provided as Supplementary Data 1–4.

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Acknowledgements

D.J. gratefully acknowledges funding from Singapore MOE Tier 2 grants (T2EP10220-0004 and T2EP10221-0012), Singapore MOE Tier 1 grants (A-0008368-00-00 and A-0008369-00-00) and a Singapore A*STAR grant (U2102d2004). T.C.S. gratefully acknowledges funding from Singapore MOE Tier 2 grants (MOE2019-T2-1-097 and MOE-T2EP50120-0004) and a National Research Foundation Singapore NRF Investigatorship (NRF-NRFI-2018-04). We thank J.W. for the use of a flow pump, N.Y. for DRIFTS, L.Q. for the measurement of contact angle and C.X. for providing the g-C3N4 sample.

Author information

Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, National University of Singapore, Singapore, Singapore

    Yongzhi Chen, Ruoyang Liu & Donglin Jiang

  2. Division of Physics and Applied Physics, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore, Singapore

    Yuanyuan Guo & Tze Chien Sum

  3. Institute of High Performance Computing, Agency for Science, Technology and Research, Singapore, Singapore

    Gang Wu & Shuo Wang Yang

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  1. Yongzhi Chen
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Contributions

D.J. conceived the idea and led the project. Y.C. and R.L. conducted the experiments and measurements. Y.G. and T.C.S. conducted the transient absorption measurements. G.W. and W.Y. performed the calculations. Y.C., R.L., Y.G., G.W., T.C.S., S.W.Y. and D.J. interpreted the results and Y.C. and D.J. wrote the paper. All authors have read and commented on the paper.

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Correspondence to Donglin Jiang.

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Nature Synthesis thanks Pascal Van Der Voort and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alison Stoddart, in collaboration with the Nature Synthesis team.

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Extended data

Extended Data Fig. 1 Electrostatic potential distribution.

a–c, Electrostatic potential maps for TP-DPBD1O-COF (a), TP-DPBD2O-COF (b) and TP-DPBD3O-COF (c).

Extended Data Fig. 2 Photocatalytic pathway.

a, Active site of diphenylbutadiyne linker for oxygen reduction reaction. b, Photocatalytic cycle for oxygen reduction reaction over butadiyne unit of the linker. c, Active site for water oxidation reaction at the triphenylene knot. d, Photocatalytic cycle for water oxidation over the phenyl unit of the knot.

Supplementary Information

Supplementary Information

Materials and methods, synthetic procedures, Supplementary Tables 1–6 and Figs. 1–60.

Supplementary Video

Supplementary Videos 1–4

Supplementary Data 1

Refined crystal structure of TP-DPBD1O-COF.

Supplementary Data 2

Refined crystal structure of TP-DPBD1O-COF.

Supplementary Data 3

Refined crystal structure of TP-DPBD3O-COF.

Supplementary Data 4

Refined crystal structure of TP-QPh-COF.

Source data

Source Data Fig. 3

Statistical source data.

Source Data Fig. 4

Statistical source data.

Source Data Fig. 6

Statistical source data.

Source Data Fig. 7

Statistical source data.

Source Data Fig. 8

Statistical source data.

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Chen, Y., Liu, R., Guo, Y. et al. Hierarchical assembly of donor–acceptor covalent organic frameworks for photosynthesis of hydrogen peroxide from water and air. Nat. Synth (2024). https://doi.org/10.1038/s44160-024-00542-4

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