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Confined local oxygen gas promotes electrochemical water oxidation to hydrogen peroxide

Abstract

Electrochemical two-electron water oxidation is a promising route for renewable and on-site H2O2 generation as an alternative to the anthraquinone process. However, it is currently restricted by low selectivity due to strong competition from the traditional four-electron oxygen evolution reaction, as well as large overpotential and low production rates. Here we report an interfacial engineering approach, where by coating the catalyst with hydrophobic polymers we confine in situ produced O2 gas to tune the water oxidation reaction pathway. Using carbon catalysts as a model system, we show a significant increase of the intrinsic H2O-to-H2O2 selectivity and activity compared to that of the pristine catalyst. The maximal H2O2 Faradaic efficiency was enhanced by sixfold to 66% with an overpotential of 640 mV, under which a H2O2 production rate of 23.4 µmol min−1 cm−2 (75.2 mA cm−2 partial current) was achieved. This approach was successfully extended to nickel metal, demonstrating the wide applicability of our local gas confinement concept.

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Fig. 1: Experimental observation of local product concentration effect.
Fig. 2: Water oxidation performances on CFP and Ni-based catalysts in 1.0 M Na2CO3, pH 11.96.
Fig. 3: Possible mechanisms.
Fig. 4: Applications of developed 2e-WOR//2e-ORR H2O2 electrosynthetic cell.

Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding authors on reasonable request.

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Acknowledgements

This work was supported by Rice University. H.W. is a CIFAR Azrieli Global Scholar in the Bio-inspired Solar Energy Programme. C.X. acknowledges support from a J. Evans Attwell-Welch Postdoctoral Fellowship provided by the Smalley-Curl Institute. K.C. acknowledges a grant (9455) from VILLUM FONDEN. S.S. acknowledges the support from the University of Calgary’s Canada First Research Excellence Fund Program, the Global Research Initiative in Sustainable Low Carbon Unconventional Resources. S.R. and S.B. acknowledge funding from US Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science Program to the SUNCAT Center for Interface Science and Catalysis. This work was performed in part at the Shared Equipment Authority (SEA) at Rice University. The authors acknowledge L. Fan for the design of the scheme in Fig. 3. The authors also acknowledge Q. Jiang, T. Sun and Z. Lu for their support to the experiment and useful discussions.

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Contributions

C.X. and H.W. conceptualized the project. H.W., K.C. and S.S. supervised the project. C.X. synthesized the catalysts, conducted the catalytic tests and the related data processing, and performed materials characterization and analysis with the help of K.J., F.C. and X.S. S.B. and S.R. performed the theoretical study. C.X. and H.W. wrote the manuscript with support from all authors.

Corresponding authors

Correspondence to Samira Siahrostami, Karen Chan or Haotian Wang.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–18, Table 1, Note 1 and references.

Supplementary Dataset 1

Atomic coordinates of the optimized computational models.

Supplementary Video 1

Water oxidation of pristine GC under 2.05 V versus RHE.

Supplementary Video 2

Water oxidation of 300-GC under 2.05 V versus RHE.

Supplementary Video 3

Water oxidation of 200-GC under 2.05 V versus RHE.

Supplementary Video 4

Organic dye degradation using generated H2O2 solution.

Supplementary Video 5

Organic dye degradation using extracted solid H2O2 (Speed up, three times).

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Xia, C., Back, S., Ringe, S. et al. Confined local oxygen gas promotes electrochemical water oxidation to hydrogen peroxide. Nat Catal 3, 125–134 (2020). https://doi.org/10.1038/s41929-019-0402-8

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