Atomically dispersed manganese catalysts for oxygen reduction in proton-exchange membrane fuel cells

Abstract

Platinum group metal (PGM)-free catalysts that are also iron free are highly desirable for the oxygen reduction reaction (ORR) in proton-exchange membrane fuel cells, as they avoid possible Fenton reactions. Here we report an efficient ORR catalyst that consists of atomically dispersed nitrogen-coordinated single Mn sites on partially graphitic carbon (Mn-N-C). Evidence for the embedding of the atomically dispersed MnN4 moieties within the carbon surface-exposed basal planes was established by X-ray absorption spectroscopy and their dispersion was confirmed by aberration-corrected electron microscopy with atomic resolution. The Mn-N-C catalyst exhibited a half-wave potential of 0.80 V versus the reversible hydrogen electrode, approaching that of Fe-N-C catalysts, along with significantly enhanced stability in acidic media. The encouraging performance of the Mn-N-C catalyst as a PGM-free cathode was demonstrated in fuel cell tests. First-principles calculations further support the MnN4 sites as the origin of the ORR activity via a 4e pathway in acidic media.

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Fig. 1: Schematic of atomically dispersed MnN4 site catalyst synthesis.
Fig. 2: Structural characterization by XANES, EXAFS and XPS.
Fig. 3: Morphology and atomic structure of the 20Mn-NC-second catalyst.
Fig. 4: ORR activity studied by using RRDE and fuel cell tests.
Fig. 5: Catalyst stability studied by using potential cycling and constant potentials.
Fig. 6: Fundamental understanding of possible Mn active sites by using DFT calculations.

Data availability

The data that support the findings of this study are available from the primary corresponding author (G.Wu) upon reasonable request.

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Acknowledgements

G.Wu thanks the Research and Education in eNergy, Environment and Water (RENEW) program at the University at Buffalo, SUNY and National Science Foundation (CBET-1604392, 1804326) for partial financial support. G.Wu, G.Wang and H.X. acknowledge support from the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Fuel Cell Technologies Office (DE-EE0008075). Electron microscopy research was conducted at Oak Ridge National Laboratory’s Center for Nanophase Materials Sciences of (D.A.C. and K.L.M) and the Center for Functional Nanomaterials at Brookhaven National Laboratory (S.H. and D.S., under contract No. DE-SC0012704), which both are US DOE Office of Science User Facilities. XAS measurements were performed at beamline 9-BM at the Advanced Photon Source, a User Facility operated for the US DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357 (Z.F. and G.E.S.). Z.W. and J.L. thank the National Natural Science Foundation of China (Grant No. 21273058 and 21673064) for support.

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G.Wu, Z.W. and J. L. designed the experiments, analysed the experimental data, and wrote the manuscript. J.L., M.C. and H.Z. synthesized catalyst samples and carried out electrochemical measurements. D.A.C., K.L.M, S.H. and D.S performed electron microscopy analyses and data interpretation. S.K. conducted XPS analysis. M.W., M.L., G.E.S. and Z.F. recorded and analysed XAS data. C.L. and H.X. carried out fuel cell tests. B.L., K.L. and G.Wang conducted computational studies.

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Correspondence to Zhenbo Wang or Gang Wu.

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Supplementary Note 1, Supplementary Figures 1–30, Supplementary Tables 1–13 and Supplementary References

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Li, J., Chen, M., Cullen, D.A. et al. Atomically dispersed manganese catalysts for oxygen reduction in proton-exchange membrane fuel cells. Nat Catal 1, 935–945 (2018). https://doi.org/10.1038/s41929-018-0164-8

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