Article | Published:

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 optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

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.

Additional information

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

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).

  2. 2.

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

  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).

  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).

  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).

  6. 6.

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

  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).

  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).

  9. 9.

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

  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).

  11. 11.

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

  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).

  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).

  14. 14.

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

  15. 15.

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

  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).

  17. 17.

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

  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).

  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).

  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).

  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).

  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).

  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).

  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).

  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).

  26. 26.

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

  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).

  28. 28.

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

  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).

  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.

    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).

  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).

  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).

  34. 34.

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

  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).

  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).

  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).

  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).

  39. 39.

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

  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).

  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).

  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).

  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).

  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).

  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).

  46. 46.

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

  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).

  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).

  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).

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

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.

Competing interests

The authors declare no competing interests.

Correspondence to Qinghua Liu.

Supplementary information

  1. 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
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.