Lattice-strained metal–organic-framework arrays for bifunctional oxygen electrocatalysis

Abstract

Oxygen electrocatalysis is central to technologies such as fuel cells and electrolysers, but challenges remain due to the lack of effective earth-abundant electrocatalysts and insufficient understanding of catalytic mechanisms. Here we demonstrate that robust bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activity can be achieved by inducing lattice strain in noble-metal-free metal–organic frameworks (MOFs). Lattice-strained NiFe MOFs exhibit mass activities of 500 A gmetal−1 at a half-wave potential of 0.83 V for the ORR and 2,000 A gmetal−1 at an overpotential of 0.30 V for the OER, which are 50–100 times that of pristine NiFe metal–organic frameworks. The catalyst maintains ~97% of its initial activity after 200 h of continuous ORR/OER reaction at a high current density of 100–200 mA cm−2. Using operando synchrotron spectroscopies, we observed a key superoxide *OOH intermediate emerging on Ni4+ sites during both the ORR and OER processes, which suggests a four-electron mechanistic pathway.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Fig. 1: Structural characterizations of lattice-strained MOFs.
Fig. 2: Performance of lattice-strained MOFs for oxygen electrocatalysis.
Fig. 3: Atomic and electronic structures of lattice-strained MOFs.
Fig. 4: The formation of a superoxide intermediate and high-valence Ni4+ species during the ORR and OER.
Fig. 5: Mechanistic insight into the electrocatalytic activity of the lattice-strained MOFs.

Data availability

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

Change history

  • 19 March 2020

    An amendment to this paper has been published and can be accessed via a link at the top of the paper.

References

  1. 1.

    Stamenkovic, V. R., Strmcnik, D., Lopes, P. P. & Markovic, N. M. Energy and fuels from electrochemical interfaces. Nat. Mater. 16, 57–69 (2017).

    Google Scholar 

  2. 2.

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

    Google Scholar 

  3. 3.

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

    Google Scholar 

  4. 4.

    Chung, H. T. et al. Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst. Science 357, 479–483 (2017).

    Google Scholar 

  5. 5.

    Guo, D. H. et al. Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts. Science 351, 361–365 (2016).

    Google Scholar 

  6. 6.

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

    Google Scholar 

  7. 7.

    Yeh, T. F., Teng, C. Y., Chen, S. J. & Teng, H. S. Nitrogen-doped graphene oxide quantum dots as photocatalysts for overall water-splitting under visible light illumination. Adv. Mater. 26, 3297–3303 (2014).

    Google Scholar 

  8. 8.

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

    Google Scholar 

  9. 9.

    Bu, L. Z. et al. Biaxially strained PtPb/Pt core/shell nanoplate boosts oxygen reduction catalysis. Science 354, 1410–1414 (2016).

    Google Scholar 

  10. 10.

    Antolini, E. Iridium as catalyst and cocatalyst for oxygen evolution/reduction in acidic polymer electrolyte membrane electrolyzers and fuel cells. ACS Catal. 4, 1426–1440 (2014).

    Google Scholar 

  11. 11.

    Huang, J. H. et al. CoOOH nanosheets with high mass activity for water oxidation. Angew. Chem. Int. Ed. 54, 8722–8727 (2015).

    Google Scholar 

  12. 12.

    Chen, P. Z. et al. Atomically dispersed iron–nitrogen species as electrocatalysts for bifunctional oxygen evolution and reduction reactions. Angew. Chem. Int. Ed. 56, 610–614 (2017).

    Google Scholar 

  13. 13.

    Tse, E. C. M. et al. Proton transfer dynamics control the mechanism of O2 reduction by a non-precious metal electrocatalyst. Nat. Mater. 15, 754–759 (2016).

    Google Scholar 

  14. 14.

    Lee, S., Kapustin, E. A. & Yaghi, O. M. Coordinative alignment of molecules in chiral metal–organic frameworks. Science 353, 808–811 (2016).

    Google Scholar 

  15. 15.

    Sheberla, D. et al. Conductive MOF electrodes for stable supercapacitors with high areal capacitance. Nat. Mater. 16, 220–224 (2017).

    Google Scholar 

  16. 16.

    Zhao, C. M. et al. Ionic exchange of metal organic frameworks to access single nickel sites for efficient electroreduction of CO2. J. Am. Chem. Soc. 139, 8078–8081 (2017).

    Google Scholar 

  17. 17.

    Zhao, S. L. et al. Ultrathin metal–organic framework nanosheets for electrocatalytic oxygen evolution. Nat. Energy 1, 16184 (2016).

    Google Scholar 

  18. 18.

    Chmela, S., Danko, M. & Hrdlovic, P. Preparation, photochemical stability and photostabilizing efficiency of adducts of 1,8-naphthaleneimide and hindered amine stabilizers in polymer matrices. Polym. Degrad. Stab. 63, 159–164 (1999).

    Google Scholar 

  19. 19.

    Fan, L. L. et al. Atomically isolated nickel species anchored on graphitized carbon for efficient hydrogen evolution electrocatalysis. Nat. Commun. 7, 10667 (2016).

    Google Scholar 

  20. 20.

    Lu, Z. et al. Three-dimensional NiFe layered double hydroxide film for high-efficiency oxygen evolution reaction. Chem. Commun. 50, 6479–6482 (2014).

    Google Scholar 

  21. 21.

    Li, M. F. et al. Ultrafine jagged platinum nanowires enable ultrahigh mass activity for the oxygen reduction reaction. Science 354, 1414–1419 (2016).

    Google Scholar 

  22. 22.

    Gong, M. et al. An advanced Ni–Fe layered double hydroxide electrocatalyst for water oxidation. J. Am. Chem. Soc. 135, 8452–8455 (2013).

    Google Scholar 

  23. 23.

    Gorlin, M. et al. Oxygen evolution reaction dynamics, Faradaic charge efficiency, and the active metal redox states of Ni–Fe oxide water splitting electrocatalysts. J. Am. Chem. Soc. 138, 5603–5614 (2016).

    Google Scholar 

  24. 24.

    Yin, P. Q. et al. Single cobalt atoms with precise N-coordination as superior oxygen reduction reaction catalysts. Angew. Chem. Int. Ed. 55, 10800–10805 (2016).

    Google Scholar 

  25. 25.

    Liu, L. Y., Su, H., Tang, F. M., Zhao, X. & Liu, Q. H. Confined organometallic Au1Nx single-site as an efficient bifunctional oxygen electrocatalyst. Nano Energy 46, 110–116 (2018).

    Google Scholar 

  26. 26.

    Yan, W. S. et al. Valence state-dependent ferromagnetism in Mn-doped NiO thin films. Adv. Mater. 24, 353–357 (2012).

    Google Scholar 

  27. 27.

    Sun, Z. H. et al. Graphene activating room-temperature ferromagnetic exchange in cobalt-doped ZnO dilute magnetic semiconductor quantum dots. ACS Nano 8, 10589–10596 (2014).

    Google Scholar 

  28. 28.

    Petrie, J. R. et al. Enhanced bifunctional oxygen catalysis in strained LaNiO3 perovskites. J. Am. Chem. Soc. 138, 2488–2491 (2016).

    Google Scholar 

  29. 29.

    Liu, J. K. et al. Electron delocalization boosting highly efficient electrocatalytic water oxidation in layered hydrotalcites. J. Phys. Chem. C 121, 21962–21968 (2017).

    Google Scholar 

  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).

    Google Scholar 

  31. 31.

    Zheng, X. L. et al. Theory-driven design of high-valence metal sites for water oxidation confirmed using in situ soft X-ray absorption. Nat. Chem. 10, 149–154 (2018).

    Google Scholar 

  32. 32.

    Wang, L. B. et al. Incorporating nitrogen atoms into cobalt nanosheets as a strategy to boost catalytic activity toward CO2 hydrogenation. Nat. Energy 2, 869–876 (2017).

    Google Scholar 

  33. 33.

    Barraclough, C. G., Lawrance, G. A. & Lay, P. A. Characterization of binuclear μ-peroxo and μ-superoxo cobalt(iii) amine complexes from Raman spectroscopy. Inorg. Chem. 17, 3317–3322 (1978).

    Google Scholar 

  34. 34.

    Shibahara, T. & Mori, M. Raman and infrared spectra of μ-O2 dicobalt(iii) complexes. Bull. Chem. Soc. Jpn 51, 1374–1379 (1978).

    Google Scholar 

  35. 35.

    Sivasankar, N., Weare, W. W. & Frei, H. Direct observation of a hydroperoxide surface intermediate upon visible light-driven water oxidation at an Ir oxide nanocluster catalyst by rapid-scan FT-IR spectroscopy. J. Am. Chem. Soc. 133, 12976–12979 (2011).

    Google Scholar 

  36. 36.

    Nakamura, R., Imanishi, A., Murakoshi, K. & Nakato, Y. In situ FTIR studies of primary intermediates of photocatalytic reactions on nanocrystalline TiO2 films in contact with aqueous solutions. J. Am. Chem. Soc. 125, 7443–7450 (2003).

    Google Scholar 

  37. 37.

    Zandi, O. & Hamann, T. W. Determination of photoelectrochemical water oxidation intermediates on haematite electrode surfaces using operando infrared spectroscopy. Nat. Chem. 8, 778–783 (2016).

    Google Scholar 

  38. 38.

    Vanveenendaal, M. A. & Sawatzky, G. A. Doping dependence of Ni 2p X-ray-absorption spectra of MxNi1–xO (M = Li,Na). Phys. Rev. B 50, 11326–11331 (1994).

    Google Scholar 

  39. 39.

    Dey, S. et al. Molecular electrocatalysts for the oxygen reduction reaction. Nat. Rev. Chem. 1, 0098 (2017).

    Google Scholar 

  40. 40.

    Zhu, Y. P., Guo, C. X., Zheng, Y. & Qiao, S. Z. Surface and interface engineering of noble-metal-free electrocatalysts for efficient energy conversion processes. Acc. Chem. Res. 50, 915–923 (2017).

    Google Scholar 

  41. 41.

    Pegis, M. L., Wise, C. F., Martin, D. J. & Mayer, J. M. Oxygen reduction by homogeneous molecular catalysts and electrocatalysts. Chem. Rev. 118, 2340–2391 (2018).

    Google Scholar 

  42. 42.

    Brodsky, C. N. et al. In situ characterization of cofacial Co(iv) centers in Co4O4 cubane: modeling the high-valent active site in oxygen-evolving catalysts. Proc. Natl Acad. Sci. USA 114, 3855–3860 (2018).

    Google Scholar 

  43. 43.

    Xiao, H., Shin, H. & Goddard, W. A. III 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).

    Google Scholar 

  44. 44.

    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).

    Google Scholar 

  45. 45.

    Nellist, M. R. et al. Potential-sensing electrochemical atomic force microscopy for in operando analysis of water-splitting catalysts and interfaces. Nat. Energy 3, 46–52 (2018).

    Google Scholar 

  46. 46.

    Dey, S. et al. Molecular electrocatalysts for the oxygen reduction reaction. Nat. Rev. Chem. 1, 0098 (2017).

    Google Scholar 

  47. 47.

    Zhang, W., Lai, W. Z. & Cao, R. Energy-related small molecule activation reactions: oxygen reduction and hydrogen and oxygen evolution reactions catalyzed by porphyrin- and corrole-based systems. Chem. Rev. 117, 3717–3797 (2017).

    Google Scholar 

  48. 48.

    Han, Y. Z., Wu, Y. Z., Lai, W. Z. & Cao, R. Electrocatalytic water oxidation by a water-soluble nickel porphyrin complex at neutral pH with low overpotential. Inorg. Chem. 54, 5604–5613 (2015).

    Google Scholar 

  49. 49.

    Usov, P. M. et al. Cooperative electrochemical water oxidation by Zr nodes and Ni–porphyrin linkers of a PCN-224 MOF thin film. J. Mater. Chem. A 4, 16818–16823 (2016).

    Google Scholar 

Download references

Acknowledgements

This work was supported by the National Key Research and Development Programme of China (grant nos 2017YFA0402800), the National Natural Science Foundation of China (grant no. U1532265, 11875257, 21603207, 11621063 and 21533007), and the Fundamental Research Funds for the Central Universities (grant nos WK2310000054 and WK2310000070).

Author information

Affiliations

Authors

Contributions

Q.L. and W.Cheng conceived the project. W.Cheng, X.Z. and H.S. carried out the experiments. Q.L., F.T., W.Che and H.Z. analysed the experimental data. All authors contributed to writing the manuscript.

Corresponding author

Correspondence to Qinghua Liu.

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 Figures 1–37, Supplementary Tables 1–3, Supplementary Notes 1–2

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Cheng, W., Zhao, X., Su, H. et al. Lattice-strained metal–organic-framework arrays for bifunctional oxygen electrocatalysis. Nat Energy 4, 115–122 (2019). https://doi.org/10.1038/s41560-018-0308-8

Download citation

Further reading