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Chemical and structural origin of lattice oxygen oxidation in Co–Zn oxyhydroxide oxygen evolution electrocatalysts

Abstract

The oxygen evolution reaction (OER) is a key process in electrochemical energy conversion devices. Understanding the origins of the lattice oxygen oxidation mechanism is crucial because OER catalysts operating via this mechanism could bypass certain limitations associated with those operating by the conventional adsorbate evolution mechanism. Transition metal oxyhydroxides are often considered to be the real catalytic species in a variety of OER catalysts and their low-dimensional layered structures readily allow direct formation of the O–O bond. Here, we incorporate catalytically inactive Zn2+ into CoOOH and suggest that the OER mechanism is dependent on the amount of Zn2+ in the catalyst. The inclusion of the Zn2+ ions gives rise to oxygen non-bonding states with different local configurations that depend on the quantity of Zn2+. We propose that the OER proceeds via the lattice oxygen oxidation mechanism pathway on the metal oxyhydroxides only if two neighbouring oxidized oxygens can hybridize their oxygen holes without sacrificing metal–oxygen hybridization significantly, finding that Zn0.2Co0.8OOH has the optimum activity.

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Acknowledgements

The authors appreciate the support from the National Research Foundation, Prime Minister’s Office, Singapore, under its Campus for Research Excellence and Technological Enterprise (CREATE) programme. We also acknowledge financial support from the academic research fund AcRF Tier 2 (M4020246, ARC10/15), Ministry of Education, Singapore.

Author information

X.W., Z.J.X. and Z.-F.H. designed the studies and wrote the paper. Z.-F.H. synthesized the catalysts and performed the catalytic tests. Z.-F.H. and J.S. performed the density functional theory calculations. Z.-F.H., S.D., C.W. and J.M.V.N. conducted the SEM, STEM-EELS and XPS measurements. Y.D. and S.X. conducted the XAFS measurements. All authors discussed the results and commented on the manuscript.

Competing interests

The authors declare no competing interests.

Correspondence to Zhichuan J. Xu or Xin Wang.

Supplementary information

Supplementary Information

Supplementary Methods, Supplementary Tables 1–7, Supplementary Figures 1–25, Supplementary References

Supplementary Data 1

POSCAR data for CoO2 and zinc-substituted CoO2 models.

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Fig. 1: Formation of oxygen holes in ONB.
Fig. 2: Correlation of the OER mechanism with the different local configurations.
Fig. 3: Design and structural characterization of zinc-substituted CoOOH.
Fig. 4: Electrocatalytic OER measurements.
Fig. 5: Chemical recognition of peroxo-like species from the LOM.