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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 ( (ref. 31).


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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.

Corresponding authors

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

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The authors declare no competing interests.

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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 3, 985–992 (2020).

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