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Origins of enhanced oxygen reduction activity of transition metal nitrides

Nature Materials volume 23, pages 1695–1703 (2024)Cite this article

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Abstract

Transition metal nitride (TMN-) based materials have recently emerged as promising non-precious-metal-containing electrocatalysts for the oxygen reduction reaction (ORR) in alkaline media. However, the lack of fundamental understanding of the oxide surface has limited insights into structure–(re)activity relationships and rational catalyst design. Here we demonstrate how a well-defined TMN can dictate/control the as-formed oxide surface and the resulting ORR electrocatalytic activity. Structural characterization of MnN nanocuboids revealed that an electrocatalytically active Mn3O4 shell grew epitaxially on the MnN core, with an expansive strain along the [010] direction to the surface Mn3O4. The strained Mn3O4 shell on the MnN core exhibited an intrinsic activity that was over 300% higher than that of pure Mn3O4. A combined electrochemical and computational investigation indicated/suggested that the enhancement probably originates from a more hydroxylated oxide surface resulting from the expansive strain. This work establishes a clear and definitive atomistic picture of the nitride/oxide interface and provides a comprehensive mechanistic understanding of the structure–reactivity relationship in TMNs, critical for other catalytic interfaces for different electrochemical processes.

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Fig. 1: Physicochemical characterization of as-synthesized MnN/C catalysts.
Fig. 2: Electrochemical evaluation of MnN/C as ORR catalysts in alkaline medium.
Fig. 3: Operando/in situ spectroscopic studies of MnN/C under electrochemical conditions.
Fig. 4: Atomic model and strain analysis based on STEM imaging.
Fig. 5: DFT calculations to understand the strain effects on ORR performance.

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Data availability

The data supporting the findings of this study are included in the published article and its Supplementary Information or available from the corresponding authors on request. Source data are provided with this paper.

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Acknowledgements

This work was supported by the Center for Alkaline Based Energy Solutions (CABES), part of the Energy Frontier Research Center (EFRC) programme supported by the US Department of Energy under Grant DE-SC-0019445 (R.Z., H.L., Z.S., L.X., W.X., H.W., Q.L., M.M., D.M., H.D.A.). This work made use of TEM facilities at the Cornell Center for Materials Research (CCMR), which are supported through the National Science Foundation Materials Research Science and Engineering Center (NSF MRSEC) programme (DMR1719875, Z.S., D.M.) and PARADIM, an NSF MIP (DMR-2039380, Z.S., D.M.). This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the US Department of Energy under Contract DE-AC02-05CH11231 (L.X., M.M.) using NERSC award BES-ERCAP0022773. The in situ Raman measurement is supported by the Air Force Office of Scientific Research under award numbers FA9550-18-1-0420 (J.M, T.L.) This work is based on research conducted at the Center for High-Energy X-ray Sciences (CHEXS), which is supported by the National Science Foundation (BIO, ENG and MPS Directorates) under award DMR-1829070 (C.J.P.). We thank F. J. DiSalvo for helpful suggestions on material synthesis. We are also grateful to J. Grazul and M. Thomas at CCMR for the help in STEM training. We appreciate the assistance of Cornell High Energy Synchrotron Source staff scientists at the PIPOXS beamline, L. Debefve and K. D. Finkelstein.

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Author notes

  1. These authors contributed equally: Rui Zeng, Huiqi Li, Zixiao Shi, Lang Xu.

Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY, USA

    Rui Zeng, Huiqi Li, Zixiao Shi, Weixuan Xu, Hongsen Wang, Qihao Li & Héctor D. Abruña

  2. Department of Chemical & Biological Engineering, University of Wisconsin–Madison, Madison, WI, USA

    Lang Xu & Manos Mavrikakis

  3. Department of Chemistry, Emory University, Atlanta, GA, USA

    Jinhui Meng & Tianquan Lian

  4. Cornell High Energy Synchrotron Source, Wilson Laboratory, Cornell University, Ithaca, NY, USA

    Christopher J. Pollock

  5. School of Applied and Engineering Physics, Cornell University, Ithaca, NY, USA

    David A. Muller

  6. Kavli Institute at Cornell for Nanoscale Science, Cornell University, Ithaca, NY, USA

    David A. Muller

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Contributions

R.Z., H.L. and H.D.A. conceived and designed the experiments. R.Z. and H.L. performed sample preparation, XRD, XAS and X-ray photoemission spectroscopy characterization and the electrochemical measurements with assistance from H.W. Z.S. conducted STEM-EELS characterization and strain analysis, supervised by D.M. R.Z. and H.L. performed operando XAS characterization and data analysis with the help of W.X. and C.J.P. J.M. carried out in situ Raman spectroscopy characterization and data analysis, supervised by T.L. L.X. and M.M. conceived and designed the modelling work and L.X. performed the DFT calculations. R.Z. and H.L. carried out membrane electrode assembly testing with the help of Q.L. R.Z., H.L., Z.S., L.X., M.M. and H.D.A. wrote the paper. All of the authors discussed the results and commented on the paper.

Corresponding authors

Correspondence to Tianquan Lian, Manos Mavrikakis, David A. Muller or Héctor D. Abruña.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–38, Tables 1–5, Notes and Methods.

Supplementary Data 1

VASP optimized structures for adsorption on unstrained Mn3O4(001) surface, 5% expanded Mn3O4(001) surface and 5% compressed Mn3O4(001) surface.

Source data

Source Data Fig. 1

Density of states data plotted in Fig. 1a, XRD data plotted in Fig. 1b, XANES data plotted in Fig. 1c and EXAFS data plotted in Fig. 1d.

Source Data Fig. 2

Electrochemical data plotted in Fig. 2.

Source Data Fig. 3

XANES and EXAFS data plotted in Fig. 3a–d and Raman data plotted in Fig. 3e.

Source Data Fig. 4

In-plane strain data plotted in Fig. 4f.

Source Data Fig. 5

Gibbs free-energy data plotted in Fig. 5a and differential binding energy plotted in Fig. 5b.

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Zeng, R., Li, H., Shi, Z. et al. Origins of enhanced oxygen reduction activity of transition metal nitrides. Nat. Mater. 23, 1695–1703 (2024). https://doi.org/10.1038/s41563-024-01998-7

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