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Metal oxyhalide-based heterogeneous catalytic water purification with ultralow H2O2 consumption

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Abstract

In the quest for advanced water treatment via Fenton and Fenton-like reactions, minimizing the hydrogen peroxide (H2O2) usage by improving its activation efficiency is a critical goal. Here we report a metal oxyhalide (MOX)-based Fenton reaction system that differs fundamentally from traditional ones in pollutant removal pathway and mechanism. The MOX/H2O2 system enables efficient coupling and polymerization of organic pollutants via mild surface direct oxidation, bypassing the generation of reactive oxygen species. As a result, pollutants are translocated and removed from water with ultralow H2O2 consumption, avoiding the formation of toxic by-products. It achieves up to 80% pollutant (50% total organic carbon) removal at a H2O2-to-pollutants molar ratio of 2:1, outperforming conventional Fenton systems, which are operated at ratios ranging from 20:1 to 1,000:1. The success of these catalytic systems is attributed to the synergistic actions of O-bridging M and X sites on the catalyst surface, which selectively activate pollutants and H2O2, respectively. The catalyst could be extended to low-cost and environmentally benign MOX materials such as BiOI, FeOCl and VOCl, and be adopted to construct a dynamic membrane filtration catalytic system for high-performance and energy-saving abatement of micropollutants in water, providing a promising water purification paradigm.

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Fig. 1: Fenton (like) configurations and performance of the MOX catalyst.
Fig. 2: Characterizations of the BiOI catalyst and its ultralow H2O2 consumption.
Fig. 3: Pollutant removal behaviour and reaction pathway analyses.
Fig. 4: Mechanism of the BiOI-based heterogeneous Fenton reaction.
Fig. 5: Active facet and reaction sites of BiOI and its reaction thermodynamics.
Fig. 6: Other MOX catalysts and the practical application evaluation.
Fig. 7: DMFCS and micro-pollutant abatement.

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All data are available in the article and Supplementary Information.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (51821006, 52192684 and 52027815 to H.-Q.Y.; 51978637 to J.-J.C.; and 52300114 to Y.-J.Z.) and the Instruments Center for Physical Science at the University of Science and Technology of China (USTC). The numerical calculations in this work were conducted on the supercomputing system in the Supercomputing Center of the USTC.

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  1. These authors contributed equally: Ying-Jie Zhang, Jia-Shu Tao.

Authors and Affiliations

  1. CAS Key Laboratory of Urban Pollutant Conversion, Department of Environmental Science and Engineering, University of Science and Technology of China, Hefei, China

    Ying-Jie Zhang, Jia-Shu Tao, Yi Hu, Gui-Xiang Huang, Yuan Pan, Wen-Wei Li, Jie-Jie Chen & Han-Qing Yu

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Contributions

Y.-J.Z. came up with the original idea. H.-Q.Y. and J.-J.C. supervised the project. Y.-J.Z., Y.H., W.-W.L., H.-Q.Y. and J.-J.C. designed the experiments. Y.-J.Z., J.-S.T. and Y.H. performed the experiments and the characterizations. G.-X.H. and Y.P. helped with the data interpretations. Y.-J.Z., W.-W.L., J.-J.C. and H.-Q.Y. wrote and revised the paper. All authors commented on the paper.

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Correspondence to Wen-Wei Li, Jie-Jie Chen or Han-Qing Yu.

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Nature Water thanks Jeonghun Kim and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Zhang, YJ., Tao, JS., Hu, Y. et al. Metal oxyhalide-based heterogeneous catalytic water purification with ultralow H2O2 consumption. Nat Water 2, 770–781 (2024). https://doi.org/10.1038/s44221-024-00281-y

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