Skip to main content
SpringerLink
Log in

Tuning oxygen vacancies in two-dimensional iron-cobalt oxide nanosheets through hydrogenation for enhanced oxygen evolution activity

  • Research Article
  • Published:
Nano Research Aims and scope Submit manuscript

Abstract

The oxygen evolution reaction (OER) represents the rate-determining step of electrocatalytic water splitting into hydrogen and oxygen. Creating oxygen vacancies and adjusting their density has proven to be an effective strategy to design high-performance OER catalysts. Herein, a hydrogenation method is applied to treat a two-dimensional (2D) iron-cobalt oxide (Fe1Co1Ox-origin), with the purpose of tuning its oxygen vacancy density. Notably, compared with Fe1Co1Ox-origin, the iron-cobalt oxide hydrogenated at 200 °C and 2.0 MPa optimized conditions exhibits a markedly improved OER activity in 1.0 M KOH (with an overpotential η of 225 mV at a current density of 10 mA·cm–2) and a rapid reaction kinetics (with a Tafel slope of 36.0 mV·dec–1). Moreover, the OER mass activity of the hydrogenated oxide is 1.9 times that of Fe1Co1Ox-origin at an overpotential of 350 mV. The experimental results, combined with density functional theory (DFT) calculations, reveal that the optimal control of oxygen vacancies in 2D Fe1Co1Ox via hydrogenation can improve the electronic conductivity and promote OH– adsorption onto nearby low-coordinated Co3+ sites, resulting in a significantly enhanced OER activity.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A. Electric field effect in atomically thin carbon films. Science 2004, 306, 666–669.

    Article  Google Scholar 

  2. Meyer, J. C.; Geim, A. K.; Katsnelson, M. I.; Novoselov, K. S.; Booth, T. J.; Roth, S. The structure of suspended graphene sheets. Nature 2007, 446, 60–63.

    Article  Google Scholar 

  3. Kibsgaard, J.; Chen, Z. B.; Reinecke, B. N.; Jaramillo, T. F. Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis. Nat. Mater. 2012, 11, 963–969.

    Article  Google Scholar 

  4. Li, G. Q.; Zhang, D.; Qiao, Q.; Yu, Y. F.; Peterson, D.; Zafar, A.; Kumar, R.; Curtarolo, S.; Hunte, F.; Shannon, S. et al. All the catalytic active sites of MoS2 for hydrogen evolution. J. Am. Chem. Soc. 2016, 138, 16632–16638.

    Article  Google Scholar 

  5. Voiry, D.; Yamaguchi, H.; Li, J. W.; Silva, R.; Alves, D. C. B.; Fujita, T.; Chen, M. W.; Asefa, T.; Shenoy, V. B.; Eda, G. et al. Enhanced catalytic activity in strained chemically exfoliated WS2 nanosheets for hydrogen evolution. Nat. Mater. 2013, 12, 850–855.

    Article  Google Scholar 

  6. Gao, M. R.; Cao, X.; Gao, Q.; Xu, Y. F.; Zheng, Y. R.; Jiang, J.; Yu, S. H. Nitrogen-doped graphene supported CoSe2 nanobelt composite catalyst for efficient water oxidation. ACS Nano 2014, 8, 3970–3978.

    Article  Google Scholar 

  7. Stern, L.-A.; Feng, L. G.; Song, F.; Hu, X. L. Ni2P as a Janus catalyst for water splitting: The oxygen evolution activity of Ni2P nanoparticles. Energy Environ. Sci. 2015, 8, 2347–2351.

    Article  Google Scholar 

  8. Jia, X. D.; Zhao, Y. F.; Chen, G. B.; Shang, L.; Shi, R.; Kang, X. F.; Waterhouse, G. I. N.; Wu, L. Z.; Tung C.-H.; Zhang, T. R. Ni3FeN nanoparticles derived from ultrathin NiFe-layered double hydroxide nanosheets: An efficient overall water splitting electrocatalyst. Adv. Energy Mater. 2016, 6, 1502585.

    Article  Google Scholar 

  9. Zhuang, L. Z.; Ge, L.; Yang, Y. S.; Li, M. R.; Jia, Y.; Yao, X. D.; Zhu, Z. H. Ultrathin iron-cobalt oxide nanosheets with abundant oxygen vacancies for the oxygen evolution reaction. Adv. Mater. 2017, 29, 1606793.

    Article  Google Scholar 

  10. Lei, F. C.; Sun, Y. F.; Liu, K. T.; Gao, S.; Liang, L.; Pan, B. C.; Xie, Y. Oxygen vacancies confined in ultrathin indium oxide porous sheets for promoted visible-light water splitting. J. Am. Chem. Soc. 2014, 136, 6826–6829.

    Article  Google Scholar 

  11. Liu, X. J.; Chang, Z.; Luo, L.; Xu, T. H.; Lei, X. D.; Liu, J. F.; Sun, X. M. Hierarchical ZnxCo3–xO4 nanoarrays with high activity for electrocatalytic oxygen evolution. Chem. Mater. 2014, 26, 1889–1895.

    Article  Google Scholar 

  12. Song, F.; Hu, X. L. Exfoliation of layered double hydroxides for enhanced oxygen evolution catalysis. Nat. Commun. 2014, 5, 4477.

    Article  Google Scholar 

  13. Friebel, D.; Louie, M. W.; Bajdich, M.; Sanwald, K. E.; Cai, Y.; Wise, A. M.; Cheng, M. J.; Sokaras, D.; Weng, T. C.; Alonso-Mori, R. et al. Identification of highly active Fe sites in (Ni, Fe)OOH for electrocatalytic water splitting. J. Am. Chem. Soc. 2015, 137, 1305–1313.

    Article  Google Scholar 

  14. Zhang, B.; Zheng, X. L.; Voznyy, O.; Comin, R.; Bajdich, M.; García-Melchor, M.; Han, L. L.; Xu, J. X.; Liu, M.; Zheng, L. R. et al. Homogeneously dispersed multimetal oxygenevolving catalysts. Science 2016, 352, 333–337.

    Article  Google Scholar 

  15. Gong, M.; Li, Y. G.; Wang, H. L.; Liang, Y. Y.; Wu, J. Z.; Zhou, J. G.; Wang, J.; Regier, T.; Wei, F.; Dai, H. J. An advanced Ni-Fe layered double hydroxide electrocatalyst for water oxidation. J. Am. Chem. Soc. 2013, 135, 8452–8455.

    Article  Google Scholar 

  16. Jia, Y. Zhang, L. Z.; Gao, G. P.; Chen, H.; Wang, B.; Zhou, J. Z.; Soo, M. T.; Hong, M.; Yan, X. C.; Qian, G. R. et al. A heterostructure coupling of exfoliated Ni-Fe hydroxide nanosheet and defective graphene as a bifunctional electrocatalyst for overall water splitting. Adv. Mater. 2017, 29, 1700017.

    Article  Google Scholar 

  17. Guo, Y. Q.; Xu, K.; Wu, C. Z.; Zhao, J. Y.; Xie, Y. Surface chemical-modification for engineering the intrinsic physical properties of inorganic two-dimensional nanomaterials. Chem. Soc. Rev. 2015, 44, 637–646.

    Article  Google Scholar 

  18. Huang, Z. F.; Wang, J.; Peng, Y. C.; Jung, C. Y.; Fisher, A.; Wang, X. Design of efficient bifunctional oxygen reduction/ evolution electrocatalyst: Recent advances and perspectives. Adv. Energy Mater. 2017, 7, 1700544.

    Article  Google Scholar 

  19. Li, Y. B.; Zhang, H. M.; Wang, Y.; Liu, P. R.; Yang, H. G.; Yao, X. D.; Wang, D.; Tang, Z. Y.; Zhao, H. J. A selfsponsored doping approach for controllable synthesis of S and N co-doped trimodal-porous structured graphitic carbon electrocatalysts. Energy Environ. Sci. 2014, 7, 3720–3726.

    Article  Google Scholar 

  20. Zheng, Y.; Jiao, Y.; Li, L. H.; Xing, T.; Chen, Y.; Jaroniec, M.; Qiao, S. Z. Toward design of synergistically active carbonbased catalysts for electrocatalytic hydrogen evolution. ACS Nano 2014, 8, 5290–5296.

    Article  Google Scholar 

  21. Liu, G. L.; Robertson, A. W.; Li, M. M.-J.; Kuo, W. C. H.; Darby, M. T.; Muhieddine, M. H.; Lin, Y.-C.; Suenaga, K.; Stamatakis, M.; Warner, J. H. et al. MoS2 monolayer catalyst doped with isolated Co atoms for the hydrodeoxygenation reaction. Nat. Chem. 2017, 9, 810–816.

    Article  Google Scholar 

  22. Qiao, B. T.; Wang, A. Q.; Yang, X. F.; Allard, L. F.; Jiang, Z.; Cui, Y. T.; Liu, J. Y.; Li, J.; Zhang, T. Single-atom catalysis of CO oxidation using Pt1/FeOx. Nat. Chem. 2011, 3, 634–641.

    Article  Google Scholar 

  23. Jia, Y.; Zhang, L. Z.; Du, A. J.; Gao, G. P.; Chen, J.; Yan, X. C.; Brown, C. L.; Yao, X. D. Defect graphene as a trifunctional catalyst for electrochemical reactions. Adv. Mater. 2016, 28, 9532–9538.

    Article  Google Scholar 

  24. Ye, G. L.; Gong, Y. J.; Lin, J. H.; Li, B.; He, Y. M.; Pantelides, S. T.; Zhou, W.; Vajtai, R.; Ajayan, P. M. Defects engineered monolayer MoS2 for improved hydrogen evolution reaction. Nano Lett. 2016, 16, 1097–1103.

    Article  Google Scholar 

  25. Chen, X. B.; Liu, L.; Yu, P. Y.; Mao, S. S. Increasing solar absorption for photocatalysis with black hydrogenated titanium dioxide nanocrystals. Science 2011, 331, 746–750.

    Article  Google Scholar 

  26. Li, H.; Tsai, C.; Koh, A. L.; Cai, L. L.; Contryman, A. W.; Fragapane, A. H.; Zhao, J. H.; Han, H. S.; Manoharan, H. C.; Abild-Pedersen, F. et al. Activating and optimizing MoS2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies. Nat. Mater. 2016, 15, 48–53.

    Article  Google Scholar 

  27. Li, G. W.; Blake, G. R.; Palstra, T. T. M. Vacancies in functional materials for clean energy storage and harvesting: The perfect imperfection. Chem. Soc. Rev. 2017, 46, 1693–1706.

    Article  Google Scholar 

  28. Wang, G. M.; Wang, H. Y.; Ling, Y. C.; Tang, Y. C.; Yang, X. Y.; Fitzmorris, R. C.; Wang, C. C.; Zhang, J. Z.; Li, Y. Hydrogen-treated TiO2 nanowire arrays for photoelectrochemical water splitting. Nano Lett. 2011, 11, 3026–3033.

    Article  Google Scholar 

  29. Xu, L.; Jiang, Q. Q.; Xiao, Z. H.; Li, X. Y.; Huo, J.; Wang, S. Y.; Dai, L. M. Plasma-engraved Co3O4 nanosheets with oxygen vacancies and high surface area for the oxygen evolution reaction. Angew. Chem., Int. Ed. 2016, 55, 5277–5281.

    Article  Google Scholar 

  30. Bao, J.; Zhang, X. D.; Fan, B.; Zhang, J. J.; Zhou, M.; Yang, W. L.; Hu, X.; Wang, H.; Pan, B. C.; Xie, Y. Ultrathin spinel-structured nanosheets rich in oxygen deficiencies for enhanced electrocatalytic water oxidation. Angew. Chem., Int. Ed. 2015, 54, 7399–7404.

    Article  Google Scholar 

  31. Xiao, Z. H.; Wang, Y.; Huang, Y.-C.; Wei, Z. X.; Dong, C.-L.; Ma, J. M.; Shen, S. H.; Li, Y. F.; Wang, S. Y. Filling the oxygen vacancies in Co3O4 with phosphorus: An ultraefficient electrocatalyst for overall water splitting. Energy Environ. Sci. 2017, 10, 2563–2569.

    Article  Google Scholar 

  32. Hadt, R. G.; Hayes, D.; Brodsky, C. N.; Ullman, A. M.; Casa, D. M.; Upton, M. H.; Nocera, D. G.; Chen, L. X. X-ray spectroscopic characterization of Co(IV) and metal-metal interactions in Co4O4: Electronic structure contributions to the formation of high-valent states relevant to the oxygen evolution reaction. J. Am. Chem. Soc. 2016, 138, 11017–11030.

    Article  Google Scholar 

  33. Wang, Y. C.; Zhou, T.; Jiang, K.; Da, P. M.; Peng, Z.; Tang, J.; Kong, B.; Cai, W. B.; Yang, Z. Q.; Zheng, G. F. Reduced mesoporous Co3O4 nanowires as efficient water oxidation electrocatalysts and supercapacitor electrodes. Adv. Energy Mater. 2014, 4, 1400696.

    Article  Google Scholar 

  34. Wang, J.; Ge, X. M.; Liu, Z. L.; Thia, L.; Yan, Y.; Xiao, W.; Wang, X. Heterogeneous electrocatalyst with molecular cobalt ions serving as the center of active sites. J. Am. Chem. Soc. 2017, 139, 1878–1884.

    Article  Google Scholar 

  35. Chen, J. M.; Chin, Y. Y.; Valldor, M.; Hu, Z. W.; Lee, J. M.; Haw, S. C.; Hiraoka, N.; Ishii, H.; Pao, C. W.; Tsuei, K. D. et al. A complete high-to-low spin state transition of trivalent cobalt ion in octahedral symmetry in SrCo0.5Ru0.5O3–δ. J. Am. Chem. Soc. 2014, 136, 1514–1519.

    Article  Google Scholar 

  36. Mashino, I.; Ohtani, E.; Hirao, N.; Mitsui, T.; Masuda, R.; Seto, M.; Sakai, T.; Takahashi, S.; Nakano, S. The spin state of iron in Fe3+-bearing Mg-perovskite and its crystal chemistry at high pressure. Am. Mineral. 2014, 99, 1555–1561.

    Article  Google Scholar 

  37. Fei, H. L.; Dong, J. C.; Arellano-Jiménez, M. J.; Ye, G. L.; Kim, N. D.; Samuel, E. L. G.; Peng, Z. W.; Zhu, Z. A.; Qin, F.; Bao, J. M. et al. Atomic cobalt on nitrogen-doped graphene for hydrogen generation. Nat. Commun. 2015, 6, 8668.

    Article  Google Scholar 

  38. Kibsgaard, J.; Jaramillo, T. F. Molybdenum phosphosulfide: An active, acid-stable, earth-abundant catalyst for the hydrogen evolution reaction. Angew. Chem., Int. Ed. 2014, 53, 14433–14437.

    Article  Google Scholar 

Download references

Acknowledgements

The financial support from ARC is highly appreciated, through ARC Discovery Project (No. DP170103317), ARC Future Fellowship (No. FT120100720) and ARC Discovery Early Career Researcher Award (No. ARC DE180101030). L. Z. Z. acknowledges the support from International Postgraduate Research Scholarship (IPRS) and UQ Centennial Scholarship (UQCent). The authors acknowledge the scientific and technical assistance of the Australian Microscopy and Microanalysis Research Facility at the UQ Centre.

Author information

Author notes

  1. Linzhou Zhuang and Yi Jia contributed equally to this work.

Authors and Affiliations

  1. School of Chemical Engineering, The University of Queensland, Brisbane, 4072, Australia

    Linzhou Zhuang, Lei Ge & Zhonghua Zhu

  2. School of Environment and Science and Queensland Micro- and Nanotechnology Centre, Griffith University, Nathan Campus, Brisbane, 4111, Australia

    Yi Jia, Xuecheng Yan & Xiangdong Yao

  3. School of Chemistry, Physics, and Mechanical Engineering, Queensland University of Technology, Gardens Point Campus, Brisbane, 4001, Australia

    Tianwei He & Aijun Du

Authors
  1. Linzhou Zhuang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yi Jia
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Tianwei He
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Aijun Du
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Xuecheng Yan
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Lei Ge
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Zhonghua Zhu
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Xiangdong Yao
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Zhonghua Zhu or Xiangdong Yao.

Electronic supplementary material

12274_2018_2050_MOESM1_ESM.pdf

Tuning oxygen vacancies in two-dimensional iron-cobalt oxide nanosheets through hydrogenation for enhanced oxygen evolution activity

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhuang, L., Jia, Y., He, T. et al. Tuning oxygen vacancies in two-dimensional iron-cobalt oxide nanosheets through hydrogenation for enhanced oxygen evolution activity. Nano Res. 11, 3509–3518 (2018). https://doi.org/10.1007/s12274-018-2050-8

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-018-2050-8

Keywords

Search

Navigation