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Solar-light-activated periodate for degradation and detoxification of highly toxic 6PPD-quinone at environmental levels

Nature Water (2024)Cite this article

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Abstract

Degradation and detoxication of highly toxic 6PPD-quinone remain great challenges due to its stable structure. Here we establish a solar-light-driven IO4− activation system for efficient degradation of 6PPD-quinone at environmental concentration levels (10–100 μg l−1), with residual concentration below 5.7 ng l−1 (detection limit) within 30 min. IO3• was determined as the primary reactive species after IO4− activation for cleavage of the highly toxic quinone structure. Single electron transfer is the most favourable route for IO3• attacking, in which single electrons achieve self-driven transfer from 6PPD-quinone to IO3• due to the maintenance of spatial inversion symmetry generated by dipole moments. Femtosecond transient absorption spectra confirmed the formation of 6PPD-quinone cationic radical (6PPD-quinone•+), which was the key reaction intermediate. This study proposes a promising technology for degradation and detoxification of highly toxic 6PPD-quinone in water and brings deep insight into the reaction mechanism within IO4− activation systems.

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Fig. 1: Schematic diagram showing the construction of the periodate activation system for degradation of 6PPD-quinone.
Fig. 2: Degradation and toxicity reduction of 6PPD-quinone by solar-light-activating periodate.
Fig. 3: The contribution and identification of reactive species on the degradation of 6PPD-quinone in the solar/IO4− system.
Fig. 4: Degradation pathway of 6PPD-quinone and typical initial reaction for destruction of quinone structure.
Fig. 5: Reactive sites of electrophilic attack and energy change for HAA and SET routes.
Fig. 6: Single electron transfer mechanism from 6PPD-quinone to IO3•.

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Data availability

All relevant data that support the findings of this study are presented in the Article and Supplementary Information. Source data are provided in this paper. The source data can also be accessed through the Figshare repository and are freely available at https://doi.org/10.6084/m9.figshare.25144124.

Code availability

The codes for structural optimization of organic compounds performed on Gaussian 16 software are provided in this paper. The initial configuration of reactants and conjectured structure of the transition state is built on GaussView. The geometrical optimization and vibrational frequency are calculated at the B3LYP/def-SVP level. Single-point energy, spin density, charge distribution and electrophilicity index are calculated for the optimized geometry at the B3LYP/def2-TZVP level. Specific analysis is completed by Multiwfn 3.8 software, combined with Visual Molecular Dynamics software.

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Acknowledgements

We thank the National Natural Science Foundation of China (52270053 (W.L.)), the National Key Research and Development Program of China (2021YFA1202500 (W.L.)), the Beijing Natural Science Foundation (8232035 (W.L.)) and the Beijing Nova Program (20220484215 (W.L.)) for financial support. The High-Performance Computing Platform of Peking University is also greatly acknowledged for DFT calculation support.

Author information

Authors and Affiliations

  1. College of Environmental Sciences and Engineering, The Key Laboratory of Water and Sediment Sciences (Ministry of Education), Peking University, Beijing, People’s Republic of China

    Long Chen, Jingrun Hu, Huixuan Zhang, Dantong Jia & Wen Liu

  2. International Joint Laboratory for Regional Pollution Control (Ministry of Education), Peking University, Beijing, People’s Republic of China

    Long Chen & Wen Liu

  3. Institute of Infrastructure and Environment, School of Engineering, The University of Edinburgh, Edinburgh, UK

    Alistair G. L. Borthwick

  4. School of Engineering, Computing and Mathematics, University of Plymouth, Plymouth, UK

    Alistair G. L. Borthwick

  5. Department of Civil and Environmental Engineering, Louisiana State University, Baton Rouge, LA, USA

    Weiliang Sun

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Contributions

L.C. and W.L. conceived the idea and designed the research. L.C., J.H. and D.J. performed the experiment including degradation kinetics, transformation products detection, radical detection and Zebrafish exposure tests. L.C. and H.Z. performed the DFT calculations. A.G.L.B. and W.S. provided constructive suggestions for the results and discussion. L.C., W.L. and A.G.L.B. contributed to writing the manuscript. All co-authors discussed the results.

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Correspondence to Wen Liu.

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Nature Water thanks Zuotai Zhang, Changha Lee, and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Texts 1–11, Tables 1–9 and Figs. 1–26.

Supplementary Data 1

Source data for Supplementary Figs. 2, 3, 4, 5, 6, 7, 9, 10, 13, 15, 17, 23, 24 and 25.

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Codes for structural optimization.

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Source data for Fig. 2a–d.

Source Data Fig. 3

Source data for Fig. 3a–d.

Source Data Fig. 5

Source data for Fig. 5c,f.

Source Data Fig. 6

Source data for Fig. 6c,d.

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Chen, L., Hu, J., Borthwick, A.G.L. et al. Solar-light-activated periodate for degradation and detoxification of highly toxic 6PPD-quinone at environmental levels. Nat Water (2024). https://doi.org/10.1038/s44221-024-00236-3

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