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Structural transformation of highly active metal–organic framework electrocatalysts during the oxygen evolution reaction

Nature Energy volume 5, pages 881–890 (2020)Cite this article

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Abstract

Metal–organic frameworks (MOFs) are increasingly being investigated as electrocatalysts for the oxygen evolution reaction (OER). Despite their promising catalytic activity, many fundamental questions concerning their structure−performance relationships—especially those regarding the roles of active species—remain to be answered. Here we show the structural transformation of a Ni0.5Co0.5-MOF-74 during the OER by operando X-ray absorption spectroscopy analysis and high-resolution transmission electron microscopy imaging. We suggest that Ni0.5Co0.5OOH0.75, with abundant oxygen vacancies and high oxidation states, forms in situ and is responsible for the high OER activity observed. The ratio of Ni to Co in the bimetallic centres alters the geometric and electronic structure of as-formed active species and in turn the catalytic activity. Based on our understanding of this system, we fabricate a Ni0.9Fe0.1-MOF that delivers low overpotentials of 198 mV and 231 mV at 10 mA cm−2 and 20 mA cm−2, respectively.

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Fig. 1: Structural characterization and electrochemical evaluation.
Fig. 2: Operando XAS characterization of Ni0.5Co0.5-MOF-74.
Fig. 3: Quantitative atomic structure evolution under the operando condition.
Fig. 4: Structural characterizations of Ni0.5Co0.5-MOF-74 during and after reaction.
Fig. 5: Understanding of activity–metal ratios correlation.
Fig. 6: Electrochemical characterization of Ni1 − xFex-MOFs.

Data availability

The authors declare that the data supporting the findings of this study are available within the paper and its Supplementary Information files.

References

  1. 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 

  2. Suntivich, J., May, K. J., Gasteiger, H. A., Goodenough, J. B. & Shao-Horn, Y. A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles. Science 334, 1383–1385 (2011).

    Google Scholar 

  3. 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 

  4. 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 

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

    Google Scholar 

  6. Wu, T. et al. Iron-facilitated dynamic active-site generation on spinel CoAl2O4 with self-termination of surface reconstruction for water oxidation. Nat. Catal. 2, 763–772 (2019).

    Google Scholar 

  7. 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).

    Google Scholar 

  8. Yang, J. et al. A multifunctional biphasic water splitting catalyst tailored for integration with high-performance semiconductor photoanodes. Nat. Mater. 16, 335–341 (2016).

    Google Scholar 

  9. Jin, S. Are metal chalcogenides, nitrides and phosphides oxygen evolution catalysts or bifunctional catalysts? ACS Energy Lett. 2, 1937–1938 (2017).

    Google Scholar 

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

    Google Scholar 

  11. Shen, J.-Q. et al. Modular and stepwise synthesis of a hybrid metal–organic framework for efficient electrocatalytic oxygen evolution. J. Am. Chem. Soc. 139, 1778–1781 (2017).

    Google Scholar 

  12. Huang, J. et al. Electrochemical exfoliation of pillared-layer metal–organic framework to boost the oxygen evolution reaction. Angew. Chem. Int. Ed. 130, 4722–4726 (2018).

    Google Scholar 

  13. Wang, X.-L. et al. Exploring the performance improvement of the oxygen evolution reaction in a stable bimetal–organic framework system. Angew. Chem. Int. Ed. 57, 9660–9664 (2018).

    Google Scholar 

  14. Liu, J., Zhu, D., Guo, C., Vasileff, A. & Qiao, S.-Z. Design strategies toward advanced MOF-derived electrocatalysts for energy-conversion reactions. Adv. Energy Mater. 7, 1700518 (2017).

    Google Scholar 

  15. He, W., Ifraemov, R., Raslin, A. & Hod, I. Room-temperature electrochemical conversion of metal–organic frameworks into porous amorphous metal sulfides with tailored composition and hydrogen evolution activity. Adv. Funct. Mater. 28, 1707244 (2018).

    Google Scholar 

  16. Liberman, I., He, W., Shimoni, R., Ifraemov, R. & Hod, I. Spatially confined electrochemical conversion of metal–organic frameworks into metal-sulfides and their in-situ electrocatalytic investigation via scanning electrochemical microscopy. Chem. Sci. 11, 180–185 (2020).

    Google Scholar 

  17. Wang, L. J. et al. Synthesis and characterization of metal–organic framework-74 containing 2, 4, 6, 8 and 10 different metals. Inorg. Chem. 53, 5881–5883 (2014).

    Google Scholar 

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

    Google Scholar 

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

    Google Scholar 

  20. Song, F. & Hu, X. Ultrathin cobalt–manganese layered double hydroxide is an efficient oxygen evolution catalyst. J. Am. Chem. Soc. 136, 16481–16484 (2014).

    Google Scholar 

  21. Yano, J. et al. X-ray damage to the Mn4Ca complex in single crystals of photosystem II: a case study for metalloprotein crystallography. Proc. Natl Acad. Sci. USA 102, 12047–12052 (2005).

    Google Scholar 

  22. Funke, H., Scheinost, A. C. & Chukalina, M. Wavelet analysis of extended X-ray absorption fine structure data. Phys. Rev. B 71, 094110 (2005).

    Google Scholar 

  23. Bediako, D. K. et al. Structure–activity correlations in a nickel-borate oxygen evolution catalyst. J. Am. Chem. Soc. 134, 6801–6809 (2012).

    Google Scholar 

  24. Jiang, J. et al. Atomic-level insight into super-efficient electrocatalytic oxygen evolution on iron and vanadium co-doped nickel (oxy)hydroxide. Nat. Commun. 9, 2885 (2018).

    Google Scholar 

  25. Kirshenbaum, K. et al. In situ visualization of Li/Ag2VP2O8 batteries revealing rate-dependent discharge mechanism. Science 347, 149–154 (2015).

    Google Scholar 

  26. Mansour, A. N. & Melendres, C. A. XAFS investigation of the structure and valency of nickel in some oxycompounds. Physica B 208-209, 583–584 (1995).

    Google Scholar 

  27. Trześniewski, 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).

    Google Scholar 

  28. Drevon, D. et al. Uncovering the role of oxygen in Ni–Fe(OxHy) electrocatalysts using in situ soft X-ray absorption spectroscopy during the oxygen evolution reaction. Sci. Rep. 9, 1532 (2019).

    Google Scholar 

  29. Wuttig, M. et al. The role of vacancies and local distortions in the design of new phase-change materials. Nat. Mater. 6, 122–128 (2006).

    Google Scholar 

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

    Google Scholar 

  31. Diaz-Morales, O., Ledezma-Yanez, I., Koper, M. T. M. & Calle-Vallejo, F. Guidelines for the rational design of Ni-based double hydroxide electrocatalysts for the oxygen evolution reaction. ACS Catal. 5, 5380–5387 (2015).

    Google Scholar 

  32. Zhu, Y. et al. Unravelling surface and interfacial structures of a metal–organic framework by transmission electron microscopy. Nat. Mater. 16, 532–536 (2017).

    Google Scholar 

  33. Görlin, 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 

  34. Friebel, D. et al. Identification of highly active Fe sites in (Ni,Fe)OOH for electrocatalytic water splitting. J. Am. Chem. Soc. 137, 1305–1313 (2015).

    Google Scholar 

  35. Smith, R. D. L. et al. Geometric distortions in nickel (oxy)hydroxide electrocatalysts by redox inactive iron ions. Energy Environ. Sci. 11, 2476–2485 (2018).

    Google Scholar 

  36. Bates, M. K., Jia, Q., Doan, H., Liang, W. & Mukerjee, S. Charge-transfer effects in Ni–Fe and Ni–Fe–Co mixed-metal oxides for the alkaline oxygen evolution reaction. ACS Catal. 6, 155–161 (2016).

    Google Scholar 

  37. Hadt, R. G. et al. 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. 138, 11017–11030 (2016).

    Google Scholar 

  38. Görlin, M. et al. Tracking catalyst redox states and reaction dynamics in Ni–Fe oxyhydroxide oxygen evolution reaction electrocatalysts: the role of catalyst support and electrolyte pH. J. Am. Chem. Soc. 139, 2070–2082 (2017).

    Google Scholar 

  39. Liu, J. et al. Free-standing single-crystalline NiFe-hydroxide nanoflake arrays: a self-activated and robust electrocatalyst for oxygen evolution. Chem. Commun. 54, 463–466 (2018).

    Google Scholar 

  40. Yang, Y., Fei, H., Ruan, G., Xiang, C. & Tour, J. M. Efficient electrocatalytic oxygen evolution on amorphous nickel–cobalt binary oxide nanoporous layers. ACS Nano 8, 9518–9523 (2014).

    Google Scholar 

  41. Shan, J., Ling, T., Davey, K., Zheng, Y. & Qiao, S.-Z. Transition-metal-doped RuIr bifunctional nanocrystals for overall water splitting in acidic environments. Adv. Mater. 31, 1900510 (2019).

    Google Scholar 

  42. Su, X. et al. Operando spectroscopic identification of active sites in NiFe Prussian blue analogues as electrocatalysts: activation of oxygen atoms for oxygen evolution reaction. J. Am. Chem. Soc. 140, 11286–11292 (2018).

    Google Scholar 

  43. Shi, Y., Yu, Y., Liang, Y., Du, Y. & Zhang, B. In site electrochemical conversion of ultrathin tannin-NiFe complex film as an efficient oxygen-evolution electrocatalyst. Angew. Chem. Int. Ed. 58, 3769–3773 (2018).

    Google Scholar 

  44. Zheng, W., Liu, M. & Lee, L. Y. S. Electrochemical instability of metal–organic frameworks: in situ spectroelectrochemical investigation of the real active sites. ACS Catal. 10, 81–92 (2020).

    Google Scholar 

  45. Miner, E. M. et al. Electrochemical oxygen reduction catalysed by Ni3(hexaiminotriphenylene)2. Nat. Commun. 7, 10942 (2016).

    Google Scholar 

  46. Görlin, M. et al. Formation of unexpectedly active Ni–Fe oxygen evolution electrocatalysts by physically mixing Ni and Fe oxyhydroxides. Chem. Commun. 55, 818–821 (2019).

    Google Scholar 

  47. Singh, C., Liberman, I., Shimoni, R., Ifaemov, R. J. & Hod, I. Pristine versus pyrolyzed metal–organic framework-based oxygen evolution electrocatalysts: evaluation of intrinsic activity using electrochemical impedance spectroscopy. Phys. Chem. Lett. 10, 3630–3636 (2019).

    Google Scholar 

  48. Trotochaud, L., Young, S. L., Ranney, J. K. & Boettcher, S. W. Nickel–iron oxyhydroxide oxygen-evolution electrocatalysts: the role of intentional and incidental iron incorporation. J. Am. Chem. Soc. 136, 6744–6753 (2014).

    Google Scholar 

  49. He, W., Gao, H.-M., Shimoni, R., Lu, Z.-Y. & Hod, I. Synergistic coupling of anionic ligands to optimize the electronic and catalytic properties of metal–organic framework-converted oxygen-evolving catalysts. ACS Appl. Energy Mater. 2, 2138–2148 (2019).

    Google Scholar 

  50. Ravel, B. & Newville, M. ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J. Synchrotron Radiat. 12, 537–541 (2005).

    Google Scholar 

  51. Sayers, D. E. & Bunker B. A. in X-ray Absorption: Principles, Applications, Techniques of EXAFS, SEXAFS and XANES (eds Koningsberger, D. C. & Prins, R.) 211–253 (Wiley, 1988).

  52. Rehr, J. J. & Albers, R. C. Theoretical approaches to X-ray absorption fine structure. Rev. Mod. Phys. 72, 621–654 (2000).

    Google Scholar 

  53. Bunău, O. & Joly, Y. Self-consistent aspects of X-ray absorption calculations. J. Phys. Condens. Matter 21, 345501–345510 (2009).

    Google Scholar 

  54. Guda, S. A. et al. Optimized finite difference method for the full-potential XANES simulations: application to molecular adsorption geometries in MOFs and metal–ligand intersystem crossing transients. J. Chem. Theory Comput. 11, 4512–4521 (2015).

    Google Scholar 

  55. Solé, V. A. et al. A multiplatform code for the analysis of energy-dispersive X-ray fluorescence spectra. Spectrochim. Acta B 62, 63–68 (2007).

    Google Scholar 

  56. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

    Google Scholar 

  57. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    Google Scholar 

  58. Kohn, W. & Sham, L. J. Self-consistent equations including exchange and correlation effects. Phys. Rev. 140, A1133–A1138 (1965).

    MathSciNet  Google Scholar 

  59. Tkalych, A. J., Zhuang, H. L. & Carter, E. A. A density functional + U assessment of oxygen evolution reaction mechanisms on β-NiOOH. ACS Catal. 7, 5329–5339 (2017).

    Google Scholar 

  60. Bajdich, M., García-Mota, M., Vojvodic, A., Nørskov, J. K. & Bell, A. T. Theoretical investigation of the activity of cobalt oxides for the electrochemical oxidation of water. J. Am. Chem. Soc. 135, 13521–13530 (2013).

    Google Scholar 

  61. Maintz, S., Deringer, V. L., Tchougréeff, A. L. & Dronskowski, R. LOBSTER: a tool to extract chemical bonding from plane‐wave based DFT. J. Comput. Chem. 37, 1030–1035 (2016).

    Google Scholar 

Download references

Acknowledgements

We appreciate financial support from the Strategic Priority Research Program of Chinese Academy of Sciences (XDB36000000, Z.T.), the National Key Basic Research Program of China (2016YFA0200700, Z.T.), the National Natural Science Foundation of China (21890381 and 21721002, Z.T.; 11605225, J.D.), the Frontier Science Key Project of Chinese Academy of Sciences (QYZDJ-SSW-SLH038, Z.T.) and K.C. Wong Education Foundation (Z.T.). S.Z. acknowledges financial support from the FH Loxton fellowship of the USYD. J.D. acknowledges support from the Youth Innovation Promotion Association, CAS. C.-T.H. acknowledges support from the Young Elite Scientists Sponsorship Program by CAST. J.Z. thanks the National Key Research and Development Program of China (2017YFA0403400). We sincerely appreciate V. Yachandra and B. Lassalle providing the XAS data for Ni(OH)2 and NiOOH references. We thank R. Chen for help and suggestions.

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Author notes

  1. These authors contributed equally: Shenlong Zhao, Chunhui Tan, Chun-Ting He.

Authors and Affiliations

  1. CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing, China

    Shenlong Zhao, Shuai Jiang, Yanfei Zhu & Zhiyong Tang

  2. School of Chemical and Biomolecular Engineering, The University of Sydney, Sydney, New South Wales, Australia

    Shenlong Zhao, Kuang-Hsu Wu, Binwei Zhang & Yuan Chen

  3. Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, China

    Chunhui Tan, Pengfei An, Haijing Li, Jing Zhang & Juncai Dong

  4. State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin, China

    Chunhui Tan & Shaoqin Liu

  5. Key Laboratory of Functional Small Organic Molecule, Ministry of Education, College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang, China

    Chun-Ting He

  6. Advanced Membranes and Porous Materials Center, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology, Thuwal, Saudi Arabia

    Feng Xie

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Contributions

Z.T. proposed the research direction and guided the project. S.Z. and J.D. designed and performed the experiments. S.Z., J.D., C.T., C.-T.H., S.L. and Z.T. analysed and discussed the experimental results and drafted the manuscript. P.A., F.X., S.J., Y.Z., K.-H.W., B.Z., H.L., J.Z. and Y.C. joined the discussion of data and gave useful suggestions. S.Z., C.T. and C.-T.H. contributed equally to this work.

Corresponding authors

Correspondence to Shaoqin Liu, Juncai Dong or Zhiyong Tang.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–51 and Tables 1–11.

Supplementary Video 1

H-type electrolyser equipped with a carbon paper-supported Ni0.9Fe0.1-MOF electrode for the oxygen evolution reaction under different applied potentials.

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Zhao, S., Tan, C., He, CT. et al. Structural transformation of highly active metal–organic framework electrocatalysts during the oxygen evolution reaction. Nat Energy 5, 881–890 (2020). https://doi.org/10.1038/s41560-020-00709-1

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