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Carbon-supported layered double hydroxide nanodots for efficient oxygen evolution: Active site identification and activity enhancement

Abstract

In this study, we developed a novel confinement-synthesis approach to layered double hydroxide nanodots (LDH-NDs) anchored on carbon nanoparticles, which formed a three-dimensional (3D) interconnected network within a porous carbon support derived from pyrolysis of metal-organic frameworks (C-MOF). The resultant LDH-NDs@C-MOF nonprecious metal catalysts were demonstrated to exhibit super-high catalytic performance for oxygen evolution reaction (OER) with excellent operation stability and low overpotential (∼230 mV) at an exchange current density of 10 mAcm−2. The observed overpotential for the LDH-NDs@C-MOF is much lower than that of large-sized LDH nanosheets (321 mV), pure carbonized MOF (411 mV), and even commercial RuO2 (281 mV). X-ray absorption measurements and density functional theory (DFT) calculations revealed partial charge transfer from Fe3+ through an O bridge to Ni2+ at the edge of LDH-NDs supported by C-MOF to produce the optimal binding energies for OER intermediates. This, coupled with a large number of exposed active sides and efficient charge and electrolyte/reactant/product transports associated with the porous 3D C-MOF support, significantly boosted the OER performance of the LDH-ND catalyst with respect to its nanosheet counterpart. Apart from the fact that this is the first active side identification for LDH-ND OER catalysts, this work provides a general strategy to enhance activities of nanosheet catalysts by converting them into edge-rich nanodots to be supported by 3D porous carbon architectures.

References

  1. [1]

    Seh, Z. W.; Kibsgaard, J.; Dickens, C. F.; Chorkendorff, I.; Nørskov, J. K.; Jaramillo, T. F. Combining theory and experiment in electrocatalysis: Insights into materials design. Science, 2017, 355, eaad4998.

    Article  Google Scholar 

  2. [2]

    Zhao, S. L.; Wang, Y.; Dong, J. C.; He, C. T.; Yin, H. J.; An, P. F.; Zhao, K.; Zhang, X. F.; Gao, C.; Zhang, L. J. et al. Ultrathin metal-organic framework nanosheets for electrocatalytic oxygen evolution. Nat. Energy 2016, 1, 16184.

    CAS  Article  Google Scholar 

  3. [3]

    Liu, X. E.; Dai, L. M. Carbon-based metal-free catalysts. Nat. Rev. Mater. 2016, 1, 16064.

    CAS  Article  Google Scholar 

  4. [4]

    Zhao, S. L.; Tan, C. H.; He, C. T.; An, P. F.; Xie, F.; Jiang, S.; Zhu, Y. F.; Wu, K. H.; Zhang, B. W.; Li, H. J. et al. Structural transformation of highly active metal-organic framework electrocatalysts during the oxygen evolution reaction. Nat. Energy 2020, 5, 881–890.

    CAS  Article  Google Scholar 

  5. [5]

    Hong, W. T.; Risch, M.; Stoerzinger, K. A.; Grimaud, A.; Suntivich, J.; Shao-Horn, Y. Toward the rational design of non-precious transition metal oxides for oxygen electrocatalysis. Energy Environ. Sci. 2015, 8, 1404–1427.

    CAS  Article  Google Scholar 

  6. [6]

    Wang, Y.; Hu, F. L.; Mi, Y.; Yan, C.; Zhao, S. L. Single-metal-atom catalysts: An emerging platform for electrocatalytic oxygen reduction. Chem. Eng. J. 2021, 406, 127135.

    CAS  Article  Google Scholar 

  7. [7]

    Fabbri, E.; Nachtegaal, M.; Binninger, T.; Cheng, X.; Kim, B. J.; Durst, J.; Bozza, F.; Graule, T.; Schäublin, R.; Wiles, L. et al. Dynamic surface self-reconstruction is the key of highly active perovskite nanoelectrocatalysts for water splitting. Nat. Mater. 2017, 16, 925–931.

    CAS  Article  Google Scholar 

  8. [8]

    Grimaud, A.; Diaz-Morales, O.; Han, B. H.; Hong, W. T.; Lee, Y. L.; Giordano, L.; Stoerzinger, K. A.; Koper, M. T. M.; Shao-Horn, Y. Activating lattice oxygen redox reactions in metal oxides to catalyse oxygen evolution. Nat. Chem. 2017, 9, 457–465.

    CAS  Article  Google Scholar 

  9. [9]

    Grimaud, A.; May, K. J.; Carlton, C. E.; Lee, Y. L.; Risch, M.; Hong, W. T.; Zhou, J. G.; Shao-Horn, Y. Double perovskites as a family of highly active catalysts for oxygen evolution in alkaline solution. Nat. Commun. 2013, 4, 2439.

    Article  CAS  Google Scholar 

  10. [10]

    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 2011, 334, 1383–1385.

    CAS  Article  Google Scholar 

  11. [11]

    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.

    CAS  Article  Google Scholar 

  12. [12]

    Yan, L. T.; Cao, L.; Dai, P. C.; Gu, X.; Liu, D. D.; Li, L. J.; Wang, Y.; Zhao, X. B. Metal-organic frameworks derived nanotube of nickel-cobalt bimetal phosphides as highly efficient electrocatalysts for overall water splitting. Adv. Funct. Mater. 2017, 27, 1703455.

    Article  CAS  Google Scholar 

  13. [13]

    Xiao, X. F.; He, C. T.; Zhao, S. L.; Li, J.; Lin, W. S.; Yuan, Z. K.; Zhang, Q.; Wang, S. Y.; Dai, L. M.; Yu, D. S. A general approach to cobalt-based homobimetallic phosphide ultrathin nanosheets for highly efficient oxygen evolution in alkaline media. Energy Environ. Sci. 2017, 10, 893–899.

    CAS  Article  Google Scholar 

  14. [14]

    Tan, Y. W.; Wang, H.; Liu, P.; Shen, Y. H.; Cheng, C.; Hirata, A.; Fujita, T.; Tang, Z.; Chen, M. W. Versatile nanoporous bimetallic phosphides towards electrochemical water splitting. Energy Environ. Sci. 2016, 9, 2257–2261.

    CAS  Article  Google Scholar 

  15. [15]

    He, P. L.; Yu, X. Y.; Lou, X. W. Carbon-incorporated nickel-cobalt mixed metal phosphide nanoboxes with enhanced electrocatalytic activity for oxygen evolution. Angew. Chem. 2017, 129, 3955–3958.

    Article  Google Scholar 

  16. [16]

    Enman, L. J.; Stevens, M. B.; Dahan, M. H.; Nellist, M. R.; Toroker, M. C.; Boettcher, S. W. Operando X-ray absorption spectroscopy shows iron oxidation is concurrent with oxygen evolution in cobalt-iron (oxy)hydroxide electrocatalysts. Angew. Chem., Int. Ed. 2018, 57, 12840–12844.

    CAS  Article  Google Scholar 

  17. [17]

    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.

    CAS  Article  Google Scholar 

  18. [18]

    Lu, X. Y.; Zhao, C. Electrodeposition of hierarchically structured three-dimensional nickel-iron electrodes for efficient oxygen evolution at high current densities. Nat. Commun. 2015, 6, 6616.

    CAS  Article  Google Scholar 

  19. [19]

    Long, X.; Li, J. K.; Xiao, S.; Yan, K. Y.; Wang, Z. L.; Chen, H. N.; Yang, S. H. A strongly coupled graphene and FeNi double hydroxide hybrid as an excellent electrocatalyst for the oxygen evolution reaction. Angew. Chem. 2014, 126, 7714–7718.

    Article  Google Scholar 

  20. [20]

    Ping, J. F.; Wang, Y. X.; Lu, Q. P.; Chen, B.; Chen, J. Z.; Huang, Y.; Ma, Q. L.; Tan, C. L.; Yang, J.; Cao, X. H. et al. Self-assembly of single-layer CoAl-layered double hydroxide nanosheets on 3D graphene network used as highly efficient electrocatalyst for oxygen evolution reaction. Adv. Mater. 2016, 28, 7640–7645.

    CAS  Article  Google Scholar 

  21. [21]

    Yang, Y. C.; Yang, Y. W.; Pei, Z. X.; Wu, K. H.; Tan, C. H.; Wang, H. Z.; Wei, L.; Mahmood, A.; Yan, C.; Dong, J. C. et al. Recent progress of carbon-supported single-atom catalysts for energy conversion and storage. Matter 2020, 3, 1442–1476.

    Article  Google Scholar 

  22. [22]

    Jiang, J.; Sun, F. F.; Zhou, S.; Hu, W.; Zhang, H.; Dong, J. C.; Jiang, Z.; Zhao, J. J.; Li, J. F.; Yan, W. S. et al. Atomic-level insight into super-efficient electrocatalytic oxygen evolution on iron and vanadium co-doped nickel (oxy)hydroxide. Nat. Commun. 2018, 9, 2885.

    Article  CAS  Google Scholar 

  23. [23]

    Cai, Z.; Zhou, D. J.; Wang, M. Y.; Bak, S. M.; Wu, Y. S.; Wu, Z. S.; Tian, Y.; Xiong, X. Y.; Li, Y. P.; Liu, W. et al. Introducing Fe2+ into nickel-iron layered double hydroxide: Local structure modulated water oxidation activity. Angew. Chem. 2018, 130, 9536–9540.

    Article  Google Scholar 

  24. [24]

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

    CAS  Article  Google Scholar 

  25. [25]

    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  CAS  Google Scholar 

  26. [26]

    Liang, H. F.; Meng, F.; Cabán-Acevedo, M.; Li, L. S.; Forticaux, A.; Xiu, L. C.; Wang, Z. C.; Jin, S. Hydrothermal continuous flow synthesis and exfoliation of NiCo layered double hydroxide nanosheets for enhanced oxygen evolution catalysis. Nano Lett. 2015, 15, 1421–1427.

    CAS  Article  Google Scholar 

  27. [27]

    Zhao, Y. F.; Zhang, X.; Jia, X. D.; Waterhouse, G. I. N.; Shi, R.; Zhang, X. R.; Zhan, F.; Tao, Y.; Wu, L. Z.; Tung, C. H. et al. Sub-3 nm ultrafine monolayer layered double hydroxide nanosheets for electrochemical water oxidation. Adv. Energy Mater. 2018, 8, 1703585.

    Article  CAS  Google Scholar 

  28. [28]

    Dresp, S.; Luo, F.; Schmack, R.; Kühl, S.; Gliech, M.; Strasser, P. An efficient bifunctional two-component catalyst for oxygen reduction and oxygen evolution in reversible fuel cells, electrolyzers and rechargeable air electrodes. Energy Environ. Sci. 2016, 9, 2020–2024.

    CAS  Article  Google Scholar 

  29. [29]

    Dang, S.; Zhu, Q. L.; Xu, Q. Nanomaterials derived from metal-organic frameworks. Nat. Rev. Mater. 2017, 3, 17075.

    Article  CAS  Google Scholar 

  30. [30]

    Chen, Y. Z.; Wang, C. M.; Wu, Z. Y.; Xiong, Y. J.; Xu, Q.; Yu, S. H.; Jiang, H. L. From bimetallic metal-organic framework to porous carbon: High surface area and multicomponent active dopants for excellent electrocatalysis. Adv. Mater. 2015, 27, 5010–5016.

    CAS  Article  Google Scholar 

  31. [31]

    Zhang, M. D.; Dai, Q. B.; Zheng, H. G.; Chen, M. D.; Dai, L. M. Novel MOF-derived Co@N-C bifunctional catalysts for highly efficient Zn-air batteries and water splitting. Adv. Mater. 2018, 30, 1705431.

    Article  CAS  Google Scholar 

  32. [32]

    Gao, R.; Yan, D. P. Fast formation of single-unit-cell-thick and defect-rich layered double hydroxide nanosheets with highly enhanced oxygen evolution reaction for water splitting. Nano Res. 2018, 11, 1883–1894.

    CAS  Article  Google Scholar 

  33. [33]

    Zhang, H.; Li, H. Y.; Akram, B.; Wang, X. Fabrication of NiFe layered double hydroxide with well-defined laminar superstructure as highly efficient oxygen evolution electrocatalysts. Nano Res. 2019, 12, 1327–1331.

    CAS  Article  Google Scholar 

  34. [34]

    Lei, Z.; Tan, Y. Y.; Zhang, Z. Y.; Wu, W.; Cheng, N. C.; Chen, R. Z.; Mu, S. C.; Sun, X. L. Defects enriched hollow porous Co-N-doped carbons embedded with ultrafine CoFe/Co nanoparticles as bifunctional oxygen electrocatalyst for rechargeable flexible solid zinc-air batteries. Nano Res. 2021, 14, 868–878.

    CAS  Article  Google Scholar 

  35. [35]

    Wang, W.; Liu, Y. C.; Li, J.; Luo, J.; Fu, L.; Chen, S. L. NiFe LDH nanodots anchored on 3D macro/mesoporous carbon as a highperformance ORR/OER bifunctional electrocatalyst. J. Mater. Chem. A 2018, 6, 14299–14306.

    CAS  Article  Google Scholar 

  36. [36]

    Wang, Q.; Shang, L.; Shi, R.; Zhang, X.; Zhao, Y. F.; Waterhouse, G. I. N.; Wu, L. Z.; Tung, C. H.; Zhang, T. R. NiFe layered double hydroxide nanoparticles on Co,N-codoped carbon nanoframes as efficient bifunctional catalysts for rechargeable zinc-air batteries. Adv. Energy. Mater. 2017, 7, 1700467.

    Article  CAS  Google Scholar 

  37. [37]

    Zhao, S. L.; Yin, H. J.; Du, L.; He, L. C.; Zhao, K.; Chang, L.; Yin, G. P.; Zhao, H. J.; Liu, S. Q.; Tang, Z. Y. Carbonized nanoscale metal-organic frameworks as high performance electrocatalyst for oxygen reduction reaction. ACS Nano 2014, 8, 12660–12668.

    CAS  Article  Google Scholar 

  38. [38]

    Yin, S. M.; Tu, W. G.; Sheng, Y.; Du, Y. H.; Kraft, M.; Borgna, A.; Xu, R. A highly efficient oxygen evolution catalyst consisting of interconnected nickel-iron-layered double hydroxide and carbon nanodomains. Adv. Mater. 2018, 30, 1705106.

    Article  CAS  Google Scholar 

  39. [39]

    Tang, C.; Wang, H. S.; Wang, H. F.; Zhang, Q.; Tian, G. L.; Nie, J. Q.; Wei, F. Spatially confined hybridization of nanometer-sized NiFe hydroxides into nitrogen-doped graphene frameworks leading to superior oxygen evolution reactivity. Adv. Mater. 2015, 27, 4516–4522.

    CAS  Article  Google Scholar 

  40. [40]

    Ma, T. Y.; Dai, S.; Jaroniec, M.; Qiao, S. Z. Metal-organic framework derived hybrid Co3O4-carbon porous nanowire arrays as reversible oxygen evolution electrodes. J. Am. Chem. Soc. 2014, 136, 13925–13931.

    CAS  Article  Google Scholar 

  41. [41]

    Zhu, X. L.; Tang, C.; Wang, H. F.; Zhang, Q.; Yang, C. H.; Wei, F. Dual-sized NiFe layered double hydroxides in situ grown on oxygen-decorated self-dispersal nanocarbon as enhanced water oxidation catalysts. J. Mater. Chem. A 2015, 3, 24540–24546.

    CAS  Article  Google Scholar 

  42. [42]

    Hou, Y.; Lohe, M. R.; Zhang, J.; Liu, S. H.; Zhuang, X. D.; Feng, X. L. Vertically oriented cobalt selenide/NiFe layered-double-hydroxide nanosheets supported on exfoliated graphene foil: An efficient 3D electrode for overall water splitting. Energy Environ. Sci. 2016, 9, 478–483.

    CAS  Article  Google Scholar 

  43. [43]

    Aijaz, A.; Masa, J.; Rösler, C.; Xia, W.; Weide, P.; Botz, A. J. R.; Fischer, R. A.; Schuhmann, W.; Muhler, M. Co@Co3O4 encapsulated in carbon nanotube-grafted nitrogen-doped carbon polyhedra as an advanced bifunctional oxygen electrode. Angew. Chem., Int. Ed. 2016, 55, 4087–4091.

    CAS  Article  Google Scholar 

  44. [44]

    Yu, L.; Zhou, H. Q.; Sun, J. Y.; Qin, F.; Yu, F.; Bao, J. M.; Yu, Y.; Chen, S.; Ren, Z. F. Cu nanowires shelled with NiFe layered double hydroxide nanosheets as bifunctional electrocatalysts for overall water splitting. Energy Environ. Sci. 2017, 10, 1820–1827.

    CAS  Article  Google Scholar 

  45. [45]

    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. 2014, 136, 6744–6753.

    CAS  Article  Google Scholar 

  46. [46]

    Chen, J. Y. C.; Dang, L. N.; Liang, H. F.; Bi, W. L.; Gerken, J. B.; Jin, S.; Alp, E. E.; Stahl, S. S. Operando analysis of NiFe and Fe oxyhydroxide electrocatalysts for water oxidation: Detection of Fe4+ by Mössbauer spectroscopy. J. Am. Chem. Soc. 2015, 137, 15090–15093.

    CAS  Article  Google Scholar 

  47. [47]

    Xu, X.; Song, F.; Hu, X. L. A nickel iron diselenide-derived efficient oxygen-evolution catalyst. Nat. Commun. 2016, 7, 12324.

    CAS  Article  Google Scholar 

  48. [48]

    Zhu, Y. P.; Ma, T.; Jaroniec, M.; Qiao, S. Z. Self-templating synthesis of hollow Co3O4 microtube arrays for highly efficient water electrolysis. Angew. Chem., Int. Ed. 2017, 56, 1324–1328.

    CAS  Article  Google Scholar 

  49. [49]

    Xie, J. F.; Zhang, X. D.; Zhang, H.; Zhang, J. J.; Li, S.; Wang, R. X.; Pan, B. C.; Xie, Y. Intralayered ostwald ripening to ultrathin nanomesh catalyst with robust oxygen-evolving performance. Adv. Mater. 2017, 29, 1604765.

    Article  CAS  Google Scholar 

  50. [50]

    Favaro, M.; Drisdell, W. S.; Marcus, M. A.; Gregoire, J. M.; Crumlin, E. J.; Haber, J. A.; Yano, J. An operando investigation of (Ni-Fe-Co-Ce)Ox system as highly efficient electrocatalyst for oxygen evolution reaction. ACS Catal. 2017, 7, 1248–1258.

    CAS  Article  Google Scholar 

  51. [51]

    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 oxygen-evolving catalysts. Science 2016, 352, 333–337.

    CAS  Article  Google Scholar 

  52. [52]

    Yeo, B. S.; Bell, A. T. In situ Raman study of nickel oxide and gold-supported nickel oxide catalysts for the electrochemical evolution of oxygen. J. Phys. Chem. C 2012, 116, 8394–8400.

    CAS  Article  Google Scholar 

  53. [53]

    Man, I. C.; Su, H. Y.; Calle-Vallejo, F.; Hansen, H. A.; Martínez, J. I.; Inoglu, N. G.; Kitchin, J.; Jaramillo, T. F.; Nørskov, J. K.; Rossmeisl, J. Universality in oxygen evolution electrocatalysis on oxide surfaces. ChemCatChem 2011, 3, 1159–1165.

    CAS  Article  Google Scholar 

  54. [54]

    Wang, Y. Y.; Zhang, Y. Q.; Liu, Z. J.; Xie, C.; Feng, S.; Liu, D. D.; Shao, M. F.; Wang, S. Y. Layered double hydroxide nanosheets with multiple vacancies obtained by dry exfoliation as highly efficient oxygen evolution electrocatalysts. Angew. Chem,. Int. Ed. 2017, 56, 5867–5871.

    CAS  Article  Google Scholar 

  55. [55]

    Li, M. T.; Zhang, L. P.; Xu, Q.; Niu, J. B.; Xia, Z. H. N-doped graphene as catalysts for oxygen reduction and oxygen evolution reactions: Theoretical considerations. J. Catal. 2014, 314, 66–72.

    CAS  Article  Google Scholar 

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Acknowledgements

S. L. Z. and L. M. D. conceived and designed the project. S. L. Z., D. T. Z., S. J., Y. C. and J. C. D. performed the experiments. S. L. Z., H. J. L., J. C. D., and Z. R. X. analysed and discussed the experimental results. L. M. D. and S. L. Z. drafted the manuscript. D.-W. W., R. A., Z. H. X., and L. M. D. joined the discussion of data and gave useful suggestions. This work was supported by The ARC (Nos. DP190103881 and FL190100126).

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Correspondence to Liming Dai.

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Carbon-supported layered double hydroxide nanodots for efficient oxygen evolution: Active site identification and activity enhancement

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Zhao, S., Zhang, D., Jiang, S. et al. Carbon-supported layered double hydroxide nanodots for efficient oxygen evolution: Active site identification and activity enhancement. Nano Res. 14, 3329–3336 (2021). https://doi.org/10.1007/s12274-021-3358-3

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Keywords

  • carbon nanomaterials
  • layered double hydroxide (LDH) nanodots
  • metal-organic framework (MOF) derivatives
  • oxygen evolution reaction