Article | Published:

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


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.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Data availability

The data that support the plots within this paper and other finding of this study are available from the corresponding authors upon reasonable request.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.


  1. 1.

    Hwang, J. et al. Perovskites in catalysis and electrocatalysis. Science 358, 751–756 (2017).

  2. 2.

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

  3. 3.

    Xia, B. Y. et al. A metal–organic framework-derived bifunctional oxygen electrocatalyst. Nat. Energy 1, 15006 (2016).

  4. 4.

    Vojvodic, A. & Norskov, J. K. Optimizing perovskites for the water-splitting reaction. Science 334, 1355–1356 (2011).

  5. 5.

    Man, I. C. et al. Universality in oxygen evolution electrocatalysis on oxide surfaces. ChemCatChem 3, 1159–1165 (2011).

  6. 6.

    Huang, Z.-F. et al. Design of efficient bifunctional oxygen reduction/evolution electrocatalyst: recent advances and perspectives. Adv. Energy Mater. 7, 1700544 (2017).

  7. 7.

    Montoya, J. H. et al. Materials for solar fuels and chemicals. Nat. Mater. 16, 70–81 (2016).

  8. 8.

    Mefford, J. T. et al. Water electrolysis on La1−xSrxCoO3 perovskite electrocatalysts. Nat. Commun. 7, 11053 (2016).

  9. 9.

    Grimaud, A. et al. Activating lattice oxygen redox reactions in metal oxides to catalyse oxygen evolution. Nat. Chem. 9, 457–465 (2017).

  10. 10.

    Rong, X., Parolin, J. & Kolpak, A. M. A fundamental relationship between reaction mechanism and stability in metal oxide catalysts for oxygen evolution. ACS Catal. 6, 1153–1158 (2016).

  11. 11.

    Yagi, S. et al. Covalency-reinforced oxygen evolution reaction catalyst. Nat. Commun. 6, 8249 (2015).

  12. 12.

    Forslund, R. P. et al. Exceptional electrocatalytic oxygen evolution via tunable charge transfer interactions in La0.5Sr1.5Ni1−xFexOδ Ruddlesden–Popper oxides. Nat. Commun. 9, 3150 (2018).

  13. 13.

    Cheng, X. et al. Oxygen evolution reaction on La1−xSrxCoO3 perovskites: a combined experimental and theoretical study of their structural, electronic, and electrochemical properties. Chem. Mater. 27, 7662–7672 (2015).

  14. 14.

    Yoo, J. S., Rong, X., Liu, Y. S. & Kolpak, A. M. Role of lattice oxygen participation in understanding trends in the oxygen evolution reaction on perovskites. ACS Catal. 8, 4628–4636 (2018).

  15. 15.

    Fabbri, E. & Schmidt, T. J. Oxygen evolution reaction—the enigma in water electrolysis. ACS Catal. 8, 9765–9774 (2018).

  16. 16.

    Nie, L. et al. Activation of surface lattice oxygen in single-atom Pt/CeO2 for low-temperature CO oxidation. Science 358, 1419–1423 (2017).

  17. 17.

    McCalla, E. et al. Visualization of O–O peroxo-like dimers in high-capacity layered oxides for Li-ion batteries. Science 350, 1516–1521 (2015).

  18. 18.

    McCrory, C. C., Jung, S., Peters, J. C. & Jaramillo, T. F. Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction. J. Am. Chem. Soc. 135, 16977–16987 (2013).

  19. 19.

    Song, F. et al. Transition metal oxides as electrocatalysts for the oxygen evolution reaction in alkaline solutions: an application-inspired renaissance. J. Am. Chem. Soc. 140, 7748–7759 (2018).

  20. 20.

    Jiao, Y., Zheng, Y., Jaroniec, M. & Qiao, S. Z. Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions. Chem. Soc. Rev. 44, 2060–2086 (2015).

  21. 21.

    Dionigi, F. & Strasser, P. NiFe-based (oxy)hydroxide catalysts for oxygen evolution reaction in non-acidic electrolytes. Adv. Energy Mater. 6, 1600621 (2016).

  22. 22.

    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).

  23. 23.

    Han, B. et al. Nanoscale structural oscillations in perovskite oxides induced by oxygen evolution. Nat. Mater. 16, 121–126 (2017).

  24. 24.

    Xu, X., Song, F. & Hu, X. A nickel iron diselenide-derived efficient oxygen-evolution catalyst. Nat. Commun. 7, 12324 (2016).

  25. 25.

    Favaro, M. et al. Understanding the oxygen evolution reaction mechanism on CoOx using operando ambient-pressure X-ray photoelectron spectroscopy. J. Am. Chem. Soc. 139, 8960–8970 (2017).

  26. 26.

    Grimaud, A., Hong, W. T., Shao-Horn, Y. & Tarascon, J. M. Anionic redox processes for electrochemical devices. Nat. Mater. 15, 121–126 (2016).

  27. 27.

    Zhou, Y. et al. Superexchange effects on oxygen reduction activity of edge-sharing [CoxMn1-xO6] octahedra in spinel oxide. Adv. Mater. 30, 1705407 (2018).

  28. 28.

    Seo, D. H. et al. The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials. Nat. Chem. 8, 692–697 (2016).

  29. 29.

    Assat, G. & Tarascon, J. M. Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries. Nat. Energy 3, 373–386 (2018).

  30. 30.

    Zhang, M., de Respinis, M. & Frei, H. Time-resolved observations of water oxidation intermediates on a cobalt oxide nanoparticle catalyst. Nat. Chem. 6, 362–367 (2014).

  31. 31.

    Maitra, U. et al. Oxygen redox chemistry without excess alkali-metal ions in Na2/3[Mg0.28Mn0.72]O2. Nat. Chem. 10, 288–295 (2018).

  32. 32.

    Shin, H., Xiao, H. & Goddard, W. A. In silico discovery of new dopants for Fe-doped Ni oxyhydroxide (Ni1−xFexOOH) catalysts for oxygen evolution reaction. J. Am. Chem. Soc. 140, 6745–6748 (2018).

  33. 33.

    Grimaud, A. et al. Activation of surface oxygen sites on an iridium-based model catalyst for the oxygen evolution reaction. Nat. Energy 2, 16189 (2016).

  34. 34.

    Yoo, J. S., Liu, Y., Rong, X. & Kolpak, A. M. Electronic origin and kinetic feasibility of the lattice oxygen participation during the oxygen evolution reaction on perovskites.J. Phys. Chem. Lett. 9, 1473–1479 (2018).

  35. 35.

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

  36. 36.

    Grimaud, A. et al. Double perovskites as a family of highly active catalysts for oxygen evolution in alkaline solution. Nat. Commun. 4, 2439 (2013).

  37. 37.

    Xie, Y., Saubanère, M. & Doublet, M. L. Requirements for reversible extra-capacity in Li-rich layered oxides for Li-ion batteries. Energy Environ. Sci. 10, 266–274 (2017).

  38. 38.

    Xiao, H., Shin, H. & Goddard, W. A. Synergy between Fe and Ni in the optimal performance of (Ni,Fe)OOH catalysts for the oxygen evolution reaction. Proc. Natl Acad. Sci. USA 115, 5872–5877 (2018).

  39. 39.

    Huang, Z.-F. et al. Hollow cobalt-based bimetallic sulfide polyhedra for efficient all-pH-value electrochemical and photocatalytic hydrogen evolution. J. Am. Chem. Soc. 138, 1359–1365 (2016).

  40. 40.

    Ye, S. H., Shi, Z. X., Feng, J. X., Tong, Y. X. & Li, G. R. Activating CoOOH porous nanosheet arrays by partial iron substitution for efficient oxygen evolution reaction. Angew. Chem. Int. Ed. 57, 2672–2676 (2018).

  41. 41.

    Huang, J. et al. Oxyhydroxide nanosheets with highly efficient electron-hole pair separation for hydrogen evolution. Angew. Chem. Int. Ed. 55, 2137–2141 (2016).

  42. 42.

    Wang, J. et al. Heterogeneous electrocatalyst with molecular cobalt ions serving as the center of active sites. J. Am. Chem. Soc. 139, 1878–1884 (2017).

  43. 43.

    Dau, H., Liebisch, P. & Haumann, M. X-ray absorption spectroscopy to analyze nuclear geometry and electronic structure of biological metal centers—potential and questions examined with special focus on the tetra-nuclear manganese complex of oxygenic photosynthesis. Anal. Bioanal. Chem. 376, 562–583 (2003).

  44. 44.

    Yang, J., Liu, H. W., Martens, W. N. & Frost, R. L. Synthesis and characterization of cobalt hydroxide, cobalt oxyhydroxide, and cobalt oxide nanodiscs. J. Phys. Chem. C 114, 111–119 (2010).

  45. 45.

    Sun, Y., Gao, S., Lei, F. & Xie, Y. Atomically-thin two-dimensional sheets for understanding active sites in catalysis. Chem. Soc. Rev. 44, 623–636 (2015).

  46. 46.

    Sun, S., Li, H. & Xu, Z. J. Impact of surface area in evaluation of catalyst activity. Joule 2, 1024–1027 (2018).

  47. 47.

    Han, L., Dong, S. & Wang, E. Transition-metal (Co, Ni, and Fe)-based electrocatalysts for the water oxidation reaction. Adv. Mater. 28, 9266–9291 (2016).

  48. 48.

    Lee, Y., Suntivich, J., May, K. J., Perry, E. E. & Shao-Horn, Y. Synthesis and activities of rutile IrO2 and RuO2 nanoparticles for oxygen evolution in acid and alkaline solutions. J. Phys. Chem. Lett. 3, 399–404 (2012).

  49. 49.

    Suen, N. T. et al. Electrocatalysis for the oxygen evolution reaction: recent development and future perspectives. Chem. Soc. Rev. 46, 337–365 (2017).

  50. 50.

    Sathiya, M. et al. Reversible anionic redox chemistry in high-capacity layered-oxide electrodes. Nat. Mater. 12, 827–835 (2013).

  51. 51.

    Gent, W. E. et al. Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides. Nat. Commun. 8, 2091 (2017).

  52. 52.

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

  53. 53.

    Giordano, L. et al. pH dependence of OER activity of oxides: current and future perspectives. Catal. Today 262, 2–10 (2016).

  54. 54.

    Liu, T. et al. Accelerating proton-coupled electron transfer of metal hydrides in catalyst model reactions. Nat. Chem. 10, 881–887 (2018).

  55. 55.

    Zhang, P. et al. Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation. Nat. Commun. 9, 381 (2018).

  56. 56.

    Yang, C., Fontaine, O., Tarascon, J. M. & Grimaud, A. Chemical recognition of active oxygen species on the surface of oxygen evolution reaction electrocatalysts. Angew. Chem. Int. Ed. 56, 8652–8656 (2017).

  57. 57.

    Trzesniewski, B. J. et al. In situ observation of active oxygen species in Fe-containing Ni-based oxygen evolution catalysts: the effect of pH on electrochemical activity. J. Am. Chem. Soc. 137, 15112–15121 (2015).

  58. 58.

    Chen, C. H. et al. Controlled synthesis of self-assembled metal oxide hollow spheres via tuning redox potentials: versatile nanostructured cobalt oxides. Adv. Mater. 20, 1205–1209 (2008).

  59. 59.

    Newville, M. IFEFFIT: interactive XAFS analysis and FEFF fitting. J. Synchrotron Radiat. 8, 322–324 (2001).

  60. 60.

    Anisimov, V. I., Aryasetiawan, F. & Lichtenstein, A. First-principles calculations of the electronic structure and spectra of strongly correlated systems: the LDA + U method. J. Phys. Condens. Matter 9, 767–808 (1997).

  61. 61.

    Anisimov, V. I., Zaanen, J. & Andersen, O. K. Band theory and Mott insulators: Hubbard U instead of Stoner I. Phys. Rev. B 44, 943 (1991).

  62. 62.

    Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).

  63. 63.

    Hammer, B., Hansen, L. B. & Nørskov, J. K. Improved adsorption energetics within density-functional theory using revised Perdew–Burke–Ernzerhof functionals. Phys. Rev. B 59, 7413 (1999).

  64. 64.

    Liao, P., Keith, J. A. & Carter, E. A. Water oxidation on pure and doped hematite (0001) surfaces: prediction of Co and Ni as effective dopants for electrocatalysis. J. Am. Chem. Soc. 134, 13296–13309 (2012).

  65. 65.

    Zhou, G. et al. First-principle study on bonding mechanism of ZnO by LDA + U method. Phys. Lett. A 368, 112–116 (2007).

  66. 66.

    Grimme, S., Ehrlich, S. & Goerigk, L. Effect of the damping function in dispersion corrected density functional theory. J. Comput. Chem. 32, 1456–1465 (2011).

  67. 67.

    Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H–Pu. J. Chem. Phys. 132, 154104 (2010).

  68. 68.

    Henkelman, G. & Jónsson, H. Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points. J. Chem. Phys. 113, 9978–9985 (2000).

  69. 69.

    Henkelman, G., Uberuaga, B. P. & Jónsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901–9904 (2000).

Download references


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.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark
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.