Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

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

Nature Energy volume 4, pages 329–338 (2019)Cite this article

Subjects

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.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

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.

Similar content being viewed by others

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.

References

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  12. Forslund, R. P. et al. Exceptional electrocatalytic oxygen evolution via tunable charge transfer interactions in La0.5Sr1.5Ni1−xFexO4±δ Ruddlesden–Popper oxides. Nat. Commun. 9, 3150 (2018).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

Download references

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

Authors and Affiliations

  1. School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore, Singapore

    Zhen-Feng Huang, Shuo Dou, Jean Marie Vianney Nsanzimana & Xin Wang

  2. School of Materials Science and Engineering, Nanyang Technological University, Singapore, Singapore

    Jiajia Song & Zhichuan J. Xu

  3. Singapore-HUJ Alliance for Research and Enterprise, NEW-CREATE Phase II, Campus for Research Excellence and Technological Enterprise (CREATE), Singapore, Singapore

    Jiajia Song

  4. Institute of Chemical and Engineering Sciences, A*STAR, Singapore, Singapore

    Yonghua Du & Shibo Xi

  5. Institute for New Energy Materials and Low-Carbon Technologies, Tianjin University of Technology, Tianjin, China

    Cheng Wang

Authors
  1. Zhen-Feng Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jiajia Song
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yonghua Du
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Shibo Xi
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Shuo Dou
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Jean Marie Vianney Nsanzimana
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Cheng Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Zhichuan J. Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Xin Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

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.

Corresponding authors

Correspondence to Zhichuan J. Xu or Xin Wang.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

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

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

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Huang, ZF., Song, J., Du, Y. et al. Chemical and structural origin of lattice oxygen oxidation in Co–Zn oxyhydroxide oxygen evolution electrocatalysts. Nat Energy 4, 329–338 (2019). https://doi.org/10.1038/s41560-019-0355-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41560-019-0355-9

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing