Ultrathin metal–organic framework nanosheets for electrocatalytic oxygen evolution

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Abstract

The design and synthesis of efficient electrocatalysts are important for electrochemical conversion technologies. The oxygen evolution reaction (OER) is a key process in such conversions, having applications in water splitting and metal–air batteries. Here, we report ultrathin metal–organic frameworks (MOFs) as promising electrocatalysts for the OER in alkaline conditions. Our as-prepared ultrathin NiCo bimetal–organic framework nanosheets on glassy-carbon electrodes require an overpotential of 250 mV to achieve a current density of 10 mA cm−2. When the MOF nanosheets are loaded on copper foam, this decreases to 189 mV. We propose that the surface atoms in the ultrathin MOF sheets are coordinatively unsaturated—that is, they have open sites for adsorption—as evidenced by a suite of measurements, including X-ray spectroscopy and density-functional theory calculations. The findings suggest that the coordinatively unsaturated metal atoms are the dominating active centres and the coupling effect between Ni and Co metals is crucial for tuning the electrocatalytic activity.

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Figure 1: Physical characterization of NiCo-UMOFNs.
Figure 2: Structural characterization of NiCo-UMOFNs.
Figure 3: OER electrochemical activity of NiCo-UMOFNs.
Figure 4: Ex situ XAS characterization of local coordination of Ni/Co atoms in NiCo-UMOFNs.
Figure 5: In situ XAS characterization of NiCo-UMOFNs.
Figure 6: DFT calculation for the OER on UMOFNs.

References

  1. 1

    Cook, T. R. et al. Solar energy supply and storage for the legacy and nonlegacy worlds. Chem. Rev. 110, 6474–6502 (2010).

  2. 2

    Smith, R. D. L. et al. Photochemical route for accessing amorphous metal oxide materials for water oxidation catalysis. Science 340, 60–63 (2013).

  3. 3

    Symes, M. D. & Cronin, L. Decoupling hydrogen and oxygen evolution during electrolytic water splitting using an electron-coupled-proton buffer. Nat. Chem. 14, 404–409 (2013).

  4. 4

    Ferreira, K. N., Iverson, T. M., Maghlaoui, K., Barber, J. & Iwata, S. Architecture of the photosynthetic oxygen-evolving center. Science 303, 1831–1838 (2004).

  5. 5

    Kanan, M. W. & Nocera, D. G. In situ formation of an oxygen-evolving catalyst in neutral water containing phosphate and Co2+. Science 321, 1072–1075 (2008).

  6. 6

    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).

  7. 7

    Sheehan, S. W. et al. A molecular catalyst for water oxidation that binds to metal oxide surfaces. Nat. Commun. 6, 6469 (2015).

  8. 8

    Mills, A. Heterogeneous redox catalysts for oxygen and chlorine evolution. Chem. Soc. Rev. 18, 285–316 (1989).

  9. 9

    Chen, G. X. et al. Interfacial effects in iron-nickel hydroxide-platinum nanoparticles enhance catalytic oxidation. Science 344, 495–499 (2014).

  10. 10

    Furukawa, H. et al. Ultrahigh porosity in metal–organic frameworks. Science 329, 424–428 (2010).

  11. 11

    Zhao, M. T. et al. Ultrathin 2D metal–organic framework nanosheets. Adv. Mater. 27, 7372–7378 (2015).

  12. 12

    Qin, J. S. et al. Ultrastable polymolybdate-based metal–organic frameworks as highly active electrocatalysts for hydrogen generation from water. J. Am. Chem. Soc. 137, 7196–7177 (2015).

  13. 13

    Kornienko, N. et al. Metal–organic frameworks for electrocatalytic reduction of carbon dioxide. J. Am. Chem. Soc. 137, 14129–14135 (2015).

  14. 14

    Kung, C.-W. et al. Metal–organic framework thin films as platforms for atomic layer deposition of cobalt ions to enable electrocatalytic water oxidation. ACS Appl. Mater. Interfaces 7, 28223–28230 (2015).

  15. 15

    Peng, Y. et al. Metal–organic framework nanosheets as building blocks for molecular sieving membranes. Science 346, 1356–1359 (2014).

  16. 16

    Rodenas, T. et al. Metal–organic framework nanosheets in polymer composite materials for gas separation. Nat. Mater. 14, 48–55 (2015).

  17. 17

    Fang, Z. L., Bueken, B., Vos, D. E. D. & Fischer, R. A. Defect-engineered metal–organic frameworks. Angew. Chem. Int. Ed. 54, 7234–7254 (2015).

  18. 18

    Liu, Y. W. et al. Low overpotential in vacancy-rich ultrathin CoSe2 nanosheets for water oxidation. J. Am. Chem. Soc. 136, 15670–15675 (2014).

  19. 19

    Lin, S. et al. Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water. Science 349, 1208–1213 (2015).

  20. 20

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

  21. 21

    Mesbah, A. et al. From hydrated Ni3(OH)2(C8H4O4)2(H2O)4 to anhydrous Ni2(OH)2(C8H4O4): impact of structural transformations on magnetic properties. Inorg. Chem. 53, 872–881 (2014).

  22. 22

    Zhuang, Z. B., Sheng, W. C. & Yan, Y. S. Synthesis of monodispere Au@Co3O4 core-shell nanocrystals and their enhanced catalytic activity for oxygen evolution reaction. Adv. Mater. 26, 3950–3955 (2014).

  23. 23

    Ma, T. Y., Dai, S., Jaroniec, M. & Qiao, S. Z. Graphitic carbon nitride nanosheet–carbon nanotube three-dimensional porous composites as high-performance oxygen evolution electrocatalysts. Angew. Chem. Int. Ed. 53, 7281–7285 (2014).

  24. 24

    Miner, E. M. et al. Electrochemical oxygen reduction catalysed by Ni3(hexaiminotriphenylene)2 . Nat. Commun. 7, 10924 (2016).

  25. 25

    Louie, M. W. & Bell, A. T. An investigation of thin-film Ni–Fe oxide catalysts for the electrochemical evolution of oxygen. J. Am. Chem. Soc. 135, 12329–12337 (2013).

  26. 26

    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 34, 12047–12052 (2005).

  27. 27

    Sarangi, R., Cho, J., Nam, W. & Solomon, E. I. XAS and DFT investigation of mononuclear cobalt (III) peroxo complexes: electronic control of the geometric structure in CoO2 versus NiO2 systems. Inorg. Chem. 50, 614–620 (2011).

  28. 28

    Trześniewski, B. J. et al. In situ observervation 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).

  29. 29

    Gorlin, Y. et al. In situ X-ray absorption spectroscopy investigation of a bifunctional manganese oxide catalyst with high activity for electrochemical water oxidation and oxygen reduction. J. Am. Chem. Soc. 135, 8525–8534 (2013).

  30. 30

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

  31. 31

    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).

  32. 32

    Su, H. Y. et al. Identifying active surface phases for metal oxide electrocatalysts: a study of manganese oxide bi-functional catalysts for oxygen reduction and water oxidation catalysis. Phys. Chem. Chem. Phys. 14, 14010–14022 (2012).

  33. 33

    Xiao, D. J. et al. Oxidation of ethane to ethanol by N2O in a metal–organic framework with coordinatively unsaturated iron (II) sites. Nat. Chem. 6, 590–595 (2014).

  34. 34

    Fu, Q. et al. Interface-confined ferrous centers for catalytic oxidation. Science 328, 1141–1144 (2010).

  35. 35

    Chen, J. Y. C. et al. Operando analysis of NiFe and Fe oxyhydroxide electrocatalysts for water oxidation: detection of Fe4+ by Mössbauer spectroscopy. J. Am. Chem. Soc. 137, 15090–15093 (2015).

  36. 36

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

  37. 37

    Lassalle-Kaiser, B. et al. Evidence from in situ X-ray absorption spectroscopy for the involvement of terminal disulfide in the reduction of protons by an amorphous molybdenum sulfide electrocatalyst. J. Am. Chem. Soc. 137, 314–321 (2015).

  38. 38

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

  39. 39

    Koningsberger, D. C. & Prins, R. X-ray Absorption: Principles, Applications, Techniques of EXAFS, SEXAFS, and XANES (eds Koningsberger, D. C. & Prins, R. ) Vol. 92 (Wiley, 1988).

  40. 40

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

  41. 41

    Joly, Y. X-ray absorption near-edge structure calculations beyond the muffin-tin approximation. Phys. Rev. B 63, 125120–125130 (2001).

  42. 42

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

  43. 43

    Kresse, G. & Furthmuller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).

  44. 44

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

  45. 45

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

  46. 46

    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 photocatalysis. J. Am. Chem. Soc. 134, 13296–13309 (2012).

  47. 47

    Alidoust, N., Lessio, M. & Carter, E. A. Cobalt (II) oxide and nickel (II) oxide alloys as potential intermediate-band semiconductors: a theoretical study. J. Appl. Phys. 119, 025102 (2016).

  48. 48

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

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Acknowledgements

We appreciate the financial support from National Research Fund for Fundamental Key Project (2014CB931801 and 2016YFA0200700, Z.T.), Instrument Developing Project of the Chinese Academy of Sciences, Grant No. YZ201311, CAS-CSIRO Cooperative Research Program, Grant No. GJHZ1503, “Strategic Priority Research Program” of the Chinese Academy of Sciences (Grant No. XDA09040100), National Natural Science Foundation of China (91023007 and 20773033 (S.L.), 21025310 (Z.T.)), and the New Century Excellent Talents in University, Outstanding Young Funding of Heilongjiang Province, Jialin Xie Fundation of Institute of High Energy Physics, CAS (542016IHEPZZBS501 (J.D.)) and NSFC (Grant No. 11605225). We thank L. Gu for providing high-angle annular dark-field scanning transmission electron microscope tests. All DFT calculations were undertaken on the NCI National Facility in Canberra, Australia, which is supported by the Australian Commonwealth Government.

Author information

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

Correspondence to Shaoqin Liu or Huijun Zhao or Zhiyong Tang.

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The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Methods, Supplementary Figures 1–41, Supplementary Tables 1–5. (PDF 4660 kb)

Supplementary Data 1

Crystallographic information for NiCo-UMOFNs. (CIF 6 kb)

Supplementary Data 2

Crystallographic information for Ni-UMOFNs. (CIF 6 kb)

Supplementary Data 3

Crystallographic information for Co-UMOFNs. (CIF 6 kb)

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Zhao, S., Wang, Y., Dong, J. et al. Ultrathin metal–organic framework nanosheets for electrocatalytic oxygen evolution. Nat Energy 1, 16184 (2016) doi:10.1038/nenergy.2016.184

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