High-valence metals improve oxygen evolution reaction performance by modulating 3d metal oxidation cycle energetics


Multimetal oxyhydroxides have recently been reported that outperform noble metal catalysts for oxygen evolution reaction (OER). In such 3d-metal-based catalysts, the oxidation cycle of 3d metals has been posited to act as the OER thermodynamic-limiting process; however, further tuning of its energetics is challenging due to similarities among the electronic structures of neighbouring 3d metal modulators. Here we report a strategy to reprogram the Fe, Co and Ni oxidation cycles by incorporating high-valence transition-metal modulators X (X = W, Mo, Nb, Ta, Re and MoW). We use in situ and ex situ soft and hard X-ray absorption spectroscopies to characterize the oxidation transition in modulated NiFeX and FeCoX oxyhydroxide catalysts, and conclude that the lower OER overpotential is facilitated by the readier oxidation transition of 3d metals enabled by high-valence modulators. We report an ~17-fold mass activity enhancement compared with that for the OER catalysts widely employed in industrial water-splitting electrolysers.

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Fig. 1: Density functional simulation findings.
Fig. 2: Oxidation state transition of 3d metal in modulated catalysts.
Fig. 3: Performance of NiFeX and FeCoX catalysts in 1 M KOH electrolyte at 25 oC.
Fig. 4: Performance of NiFeMo catalysts in industrial electrolyser systems.

Data availability

The data that support the findings of this study are available on the Zenodo platform (https://zenodo.org/record/4008830) (ref. 31).


  1. 1.

    Zhang, J., Zhao, Z., Xia, Z. & Dai, L. A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions. Nat. Nano. 10, 444–452 (2015).

    CAS  Article  Google Scholar 

  2. 2.

    Ng, J. W. D. et al. Gold-supported cerium-doped NiOx catalysts for water oxidation. Nat. Energy 1, 16053 (2016).

    CAS  Article  Google Scholar 

  3. 3.

    Liang, Y. et al. Co3O4 nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction. Nat. Mater. 10, 780–786 (2011).

    CAS  Article  Google Scholar 

  4. 4.

    Seh, Z. W. et al. Combining theory and experiment in electrocatalysis: Insights into materials design. Science 355, eaad4998 (2017).

    Article  Google Scholar 

  5. 5.

    Seitz, L. C. et al. A highly active and stable IrOx/SrIrO3 catalyst for the oxygen evolution reaction. Science 353, 1011–1014 (2016).

    CAS  Article  Google Scholar 

  6. 6.

    Bergmann, A. et al. Unified structural motifs of the catalytically active state of Co(oxyhydr)oxides during the electrochemical oxygen evolution reaction. Nat. Catal. 1, 711–719 (2018).

    CAS  Article  Google Scholar 

  7. 7.

    Guan, J. et al. Water oxidation on a mononuclear manganese heterogeneous catalyst. Nat. Catal. 1, 870–877 (2018).

    CAS  Article  Google Scholar 

  8. 8.

    Martin-Sabi, M. et al. Redox tuning the Weakley-type polyoxometalate archetype for the oxygen evolution reaction. Nat. Catal. 1, 208–213 (2018).

    CAS  Article  Google Scholar 

  9. 9.

    Roy, C. et al. Impact of nanoparticle size and lattice oxygen on water oxidation on NiFeOxHy. Nat. Catal. 1, 820–829 (2018).

    CAS  Article  Google Scholar 

  10. 10.

    Jouny, M., Luc, W. & Jiao, F. High-rate electroreduction of carbon monoxide to multi-carbon products. Nat. Catal. 1, 748–755 (2018).

    CAS  Article  Google Scholar 

  11. 11.

    Jouny, M., Luc, W. & Jiao, F. General Techno-Economic analysis of CO2 electrolysis systems. Ind. Eng. Chem. Res. 57, 2165–2177 (2018).

    CAS  Article  Google Scholar 

  12. 12.

    Galán-Mascarós, J. R. Water oxidation at electrodes modified with earth-abundant transition-metal catalysts. ChemElectroChem 2, 37–50 (2015).

    Article  Google Scholar 

  13. 13.

    Subbaraman, R. et al. Trends in activity for the water electrolyser reactions on 3d M(Ni,Co,Fe,Mn) hydr(oxy)oxide catalysts. Nat. Mater. 11, 550–557 (2012).

    CAS  Article  Google Scholar 

  14. 14.

    Roger, I., Shipman, M. A. & Symes, M. D. Earth-abundant catalysts for electrochemical and photoelectrochemical water splitting. Nat. Rev. Chem. 1, 0003 (2017).

    CAS  Article  Google Scholar 

  15. 15.

    Fabbri, E. et al. Dynamic surface self-reconstruction is the key of highly active perovskite nano-electrocatalysts for water splitting. Nat. Mater. 16, 925–931 (2017).

    CAS  Article  Google Scholar 

  16. 16.

    Zhang, B. et al. Homogeneously dispersed multimetal oxygen-evolving catalysts. Science 352, 333–337 (2016).

    CAS  Article  Google Scholar 

  17. 17.

    Rosalbino, F., Delsante, S., Borzone, G. & Scavino, G. Electrocatalytic activity of crystalline Ni–Co–M (M = Cr, Mn, Cu) alloys on the oxygen evolution reaction in an alkaline environment. Int. J. Hydrog. Energy 38, 10170–10177 (2013).

    CAS  Article  Google Scholar 

  18. 18.

    Chen, J. Y. C., Miller, J. T., Gerken, J. B. & Stahl, S. S. Inverse spinel NiFeAlO4 as a highly active oxygen evolution electrocatalyst: promotion of activity by a redox-inert metal ion. Energy Environ. Sci. 7, 1382–1386 (2014).

    CAS  Article  Google Scholar 

  19. 19.

    Gerken, J. B., Shaner, S. E., Masse, R. C., Porubsky, N. J. & Stahl, S. S. A survey of diverse earth abundant oxygen evolution electrocatalysts showing enhanced activity from Ni-Fe oxides containing a third metal. Energy Environ. Sci. 7, 2376–2382 (2014).

    CAS  Article  Google Scholar 

  20. 20.

    Friebel, D. et al. Identification of highly active Fe sites in (Ni,Fe)OOH for electrocatalytic water splitting. J. Am. Chem. Soc. 137, 1305–1313 (2015).

    CAS  Article  Google Scholar 

  21. 21.

    Bajdich, M., García-Mota, M., Vojvodic, A., Nørskov, J. K. & Bell, A. T. Theoretical investigation of the activity of cobalt oxides for the electrochemical oxidation of water. J. Am. Chem. Soc. 135, 13521–13530 (2013).

    CAS  Article  Google Scholar 

  22. 22.

    Novák, M. et al. Primary oxide minerals in the system WO3–Nb2O5–TiO2–Fe2O3–FeO and their breakdown products from the pegmatite No. 3 at Dolní Bory-Hatě, Czech Republic. Eur. J. Mineral. 20, 487–499 (2008).

    Article  Google Scholar 

  23. 23.

    Kuepper, K. et al. Electronic and magnetic properties of highly ordered Sr2FeMoO6. Phys. Stat. Sol. (a) 201, 3252–3256 (2004).

    CAS  Article  Google Scholar 

  24. 24.

    Liu, X., Yang, W. & Liu, Z. Recent progress on synchrotron-based in-situ soft X-ray spectroscopy for energy materials. Adv. Mater. 26, 7710–7729 (2014).

    CAS  Article  Google Scholar 

  25. 25.

    de Groot, F. M. F. et al. 1s2p resonant inelastic X-ray scattering of iron oxides. J. Phys. Chem. B 109, 20751–20762 (2005).

    CAS  Article  Google Scholar 

  26. 26.

    Mitsui, T. in Magmas Under Pressure (eds Kono, Y. & Sanloup, C.) 179–210 (Elsevier, 2018).

  27. 27.

    Zheng, X. et al. Theory-driven design of high-valence metal sites for water oxidation confirmed using in situ soft X-ray absorption. Nat. Chem. 10, 149–154 (2018).

    CAS  Article  Google Scholar 

  28. 28.

    Liu, P. F., Yang, S., Zheng, L. R., Zhang, B. & Yang, H. G. Mo6+ activated multimetal oxygen-evolving catalysts. Chem. Sci. 8, 3484–3488 (2017).

    CAS  Article  Google Scholar 

  29. 29.

    Liu, P. F., Yang, S., Zheng, L. R., Zhang, B. & Yang, H. G. Electrochemical etching of α-cobalt hydroxide for improvement of oxygen evolution reaction. J. Mater. Chem. A 4, 9578–9584 (2016).

    CAS  Article  Google Scholar 

  30. 30.

    Qiu, Z., Tai, C.-W., Niklasson, G. A. & Edvinsson, T. Direct observation of active catalyst surface phases and the effect of dynamic self-optimization in NiFe-layered double hydroxides for alkaline water splitting. Energy Environ. Sci. 12, 572–581 (2019).

    CAS  Article  Google Scholar 

  31. 31.

    Zhang, B. et al. High-valence metals improve OER performance by modulating 3d metal oxidation cycle energetics. Zenodo Digital Repository https://doi.org/10.5281/zenodo.4008830 (2020).

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This work was supported by MOST (grant no. 2016YFA0203302), NSFC (grant nos. 21875042, 21634003 and 51573027), STCSM (grant nos. 16JC1400702 and 18QA1400800), SHMEC (grant no. 2017-01-07-00-07-E00062) and Yanchang Petroleum Group. This work was also supported by The Programme for Professor of Eastern Scholar at Shanghai Institutions of Higher Learning. This work was supported by the Ontario Research Fund—Research Excellence Program, NSERC and the CIFAR Bio-Inspired Solar Energy program. This work has also benefited from the use of the SGM beamlines at Canadian Light Source; the 1W1B and 4B9B beamlines at the Beijing Synchrotron Radiation Facility; the BL14W1, BL08U1-A beamline at Shanghai Synchrotron Radiation Facility; and the 44A beamline at Taiwan Photon Source (TPS). Mössbauer spectroscopy measurements were conducted at the Advanced Photon Source, a Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract DE-AC02-06CH11357. We acknowledge the Paul Scherrer Institut, Villigen, Switzerland, for provision of synchrotron radiation beamtime at the beamline SuperXAS of the SLS and would like to thank M. Nachtegaal for assistance. We thank M. García-Melchor and Y. Zhang for discussions on DFT calculations. We thank J. Wu for the assistance with the TEM measurements. We thank R. Wolowiec and D. Kopilovic for their assistance. For computer time, this research used the resources of the Supercomputing Laboratory at KAUST.

Author information




E.H.S., H.P., B.Z. and L.C. supervised the project. B.Z. designed the project. L.W. and B.Z. carried out the experiments. Z.C., S.M.K. and Z.W. carried out the DFT simulations. L.W., X.Z., L. Zhang, Y.W., C.W.P., L. Zheng and J.L. carried out XAS measurements. T.R. assisted in situ XAS experiments. L.W., F.P.G.A., R.C. and J.L. performed the XAS results analysis. O.V., Z.W. and P.D.L. assisted with the DFT simulations. W.B. and E.E.A. carried out the Mössbauer spectroscopy experiment and data analysis. C.T.D. and Y.H. contributed to discussions about the experiments. Y.J. and Y.L. contributed to the discussions about DFT simulations. Y.Z. assisted with TEM and XRD measurements. B.Z., L.W., Z.C., F.P.G.A., S.M.K., H.P. and E.H.S. wrote the manuscript. All authors discussed the results and assisted during manuscript preparation.

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Correspondence to Bo Zhang or Luigi Cavallo or Huisheng Peng or Edward H. Sargent.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–41, Tables 1–4, Note and refs. 1–3.

Supplementary Data 1

Atomic coordinates of the optimized computational models.

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Zhang, B., Wang, L., Cao, Z. et al. High-valence metals improve oxygen evolution reaction performance by modulating 3d metal oxidation cycle energetics. Nat Catal (2020). https://doi.org/10.1038/s41929-020-00525-6

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