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Efficient hydrogen peroxide generation using reduced graphene oxide-based oxygen reduction electrocatalysts

Abstract

Electrochemical oxygen reduction has garnered attention as an emerging alternative to the traditional anthraquinone oxidation process to enable the distributed production of hydrogen peroxide. Here, we demonstrate a selective and efficient non-precious electrocatalyst, prepared through an easily scalable mild thermal reduction of graphene oxide, to form hydrogen peroxide from oxygen. During oxygen reduction, certain variants of the mildly reduced graphene oxide electrocatalyst exhibit highly selective and stable peroxide formation activity at low overpotentials (<10 mV) under basic conditions, exceeding the performance of current state-of-the-art alkaline catalysts. Spectroscopic structural characterization and in situ Raman spectroelectrochemistry provide strong evidence that sp2-hybridized carbon near-ring ether defects along sheet edges are the most active sites for peroxide production, providing new insight into the electrocatalytic design of carbon-based materials for effective peroxide production.

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Fig. 1: F-mrGO electrocatalytic properties for the ORR.
Fig. 2: Raman spectroelectrochemistry during ORR measurements at F-mrGO and F-mrGO(600) electrodes.
Fig. 3: Structural characterization and electrocatalytic activity of thermally annealed F-mrGO electrodes.
Fig. 4: Mass activity of different electrocatalysts for H2O2 production.

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Acknowledgements

B.D.M. and H.W.K. gratefully acknowledge support from the National Science Foundation under grant number CBET-1604927. H.W.K. also acknowledges support from the Basic Science Research Program through the National Research Foundation of Korea funded by the Ministry of Education (2016R1A6A3A03012382). N.K. gratefully acknowledges the Royal Society Newton International Fellowship. P.Y. acknowledges support from the Director of the Office of Science, Office of Basic Energy Sciences as part of the Chemical Sciences, Geosciences, and Biosciences Division of the US Department of Energy, under contract number DE-AC02-05CH11231 within the Catalysis Research Program (FWP number CH030201). The work at Molecular Foundry (XPS and scanning electron microscope) and Advanced Light Source (NEXAFS) was supported by the Office of Science, Office of Basic Energy Sciences of the US Department of Energy under contract number DE-AC02-05CH11231. H.W.K. gratefully acknowledges H. B. Park for guidance on graphene oxide synthesis, W. Kim for FTIR measurement and Y. Hwa for scanning electron microscope analysis. A. C. Luntz is also acknowledged for fruitful discussions on the potential mechanisms of ORR on mrGO materials.

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H.W.K. contributed to the experimental planning, experimental measurements, data analysis and manuscript preparation. M.B.R. and N.K. performed the Raman spectroscopy, including in situ and ex situ measurements. L.Z. measured NEXAFS. J.G. and P.Y. provided experimental guidance for the NEXAFS and Raman measurements, respectively. B.D.M. contributed to the experimental planning, data analysis and manuscript preparation. All authors reviewed and commented on the manuscript before publication.

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Correspondence to Bryan D. McCloskey.

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Kim, H.W., Ross, M.B., Kornienko, N. et al. Efficient hydrogen peroxide generation using reduced graphene oxide-based oxygen reduction electrocatalysts. Nat Catal 1, 282–290 (2018). https://doi.org/10.1038/s41929-018-0044-2

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