Activity origin and catalyst design principles for electrocatalytic hydrogen evolution on heteroatom-doped graphene


The hydrogen evolution reaction (HER) is a fundamental process in electrocatalysis and plays an important role in energy conversion through water splitting to produce hydrogen. Effective candidates for HER are often based on noble metals or transition metal dichalcogenides, while carbon-based metal-free electrocatalysts generally demonstrate poorer activity. Here we report evaluation of a series of heteroatom-doped graphene materials as efficient HER electrocatalysts by combining spectroscopic characterization, electrochemical measurements, and density functional theory calculations. Results of theoretical computations are shown to be in good agreement with experimental observations regarding the intrinsic electrocatalytic activity and the HER reaction mechanism. As a result, we establish a HER activity trend for graphene-based materials, and explore their reactivity origin to guide the design of more efficient electrocatalysts. We predict that by rationally modifying particular experimentally achievable physicochemical characteristics, a practically realizable graphene-based material will have the potential to exceed the performance of the metal-based benchmark for HER.

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Figure 1: K-edge NEXAFS spectra for heteroatom-doped graphene materials and the corresponding atomic models.
Figure 2: Hydrogen adsorption and reaction mechanism on various graphene models.
Figure 3: Electrochemical measurements and trend in intrinsic HER activity of graphene-based materials.
Figure 4: Electronic structure origins of HER activity on graphene-based materials.
Figure 5: Dual-doped graphene models and electrochemical measurements.
Figure 6: Predicted HER performance of doped graphene materials.


  1. 1

    Debe, M. K. Electrocatalyst approaches and challenges for automotive fuel cells. Nature 486, 43–51 (2012).

    Article  Google Scholar 

  2. 2

    Lewis, N. S. & Nocera, D. G. Powering the planet: chemical challenges in solar energy utilization. Proc. Natl Acad. Sci. USA 103, 15729–15735 (2006).

    Google Scholar 

  3. 3

    Barber, J. Photosynthetic energy conversion: natural and artificial. Chem. Soc. Rev. 38, 185–196 (2009).

    Article  Google Scholar 

  4. 4

    Jiao, Y., Zheng, Y., Jaroniec, M. & Qiao, S. Z. Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions. Chem. Soc. Rev. 44, 2060–2086 (2015).

    Article  Google Scholar 

  5. 5

    Nørskov, J. K., Bligaard, T., Rossmeisl, J. & Christensen, C. H. Towards the computational design of solid catalysts. Nat. Chem. 1, 37–46 (2009).

    Article  Google Scholar 

  6. 6

    Nørskov, J. K., Studt, F., Abild-Pedersen, F. & Bligaard, T. in Fundamental Concepts in Heterogeneous Catalysis 155–174 (John Wiley, 2014).

    Google Scholar 

  7. 7

    Zheng, Y., Jiao, Y., Jaroniec, M. & Qiao, S. Z. Advancing the electrochemistry of the hydrogen-evolution reaction through combining experiment and theory. Angew. Chem. Int. Ed. 54, 52–65 (2014).

    Article  Google Scholar 

  8. 8

    Cheon, J. Y. et al. Intrinsic relationship between enhanced oxygen reduction reaction activity and nanoscale work function of doped carbons. J. Am. Chem. Soc. 136, 8875–8878 (2014).

    Article  Google Scholar 

  9. 9

    Stamenkovic, V. R. et al. Improved oxygen reduction activity on Pt3Ni(111) via increased surface site availability. Science 315, 493–497 (2007).

    Article  Google Scholar 

  10. 10

    Behrens, M. et al. The active site of methanol synthesis over Cu/ZnO/Al2O3 industrial catalysts. Science 336, 893–897 (2012).

    Article  Google Scholar 

  11. 11

    Nørskov, J. K. et al. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B 108, 17886–17892 (2004).

    Article  Google Scholar 

  12. 12

    Nørskov, J. K. et al. Trends in the exchange current for hydrogen evolution. J. Electrochem. Soc. 152, J23–J26 (2005).

    Article  Google Scholar 

  13. 13

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

    Article  Google Scholar 

  14. 14

    Studt, F. et al. Discovery of a Ni-Ga catalyst for carbon dioxide reduction to methanol. Nat. Chem. 6, 320–324 (2014).

    Article  Google Scholar 

  15. 15

    Calle-Vallejo, F. et al. Finding optimal surface sites on heterogeneous catalysts by counting nearest neighbors. Science 350, 185–189 (2015).

    Article  Google Scholar 

  16. 16

    Jiao, Y., Zheng, Y., Jaroniec, M. & Qiao, S. Z. Origin of the electrocatalytic oxygen reduction activity of graphene-based catalysts: a roadmap to achieve the best performance. J. Am. Chem. Soc. 136, 4394–4403 (2014).

    Article  Google Scholar 

  17. 17

    Zheng, Y. et al. Hydrogen evolution by a metal-free electrocatalyst. Nat. Commun. 5, 3783 (2014).

    Article  Google Scholar 

  18. 18

    Sheng, W. et al. Correlating hydrogen oxidation and evolution activity on platinum at different pH with measured hydrogen binding energy. Nat. Commun. 6, 5848 (2015).

    Article  Google Scholar 

  19. 19

    Durst, J. et al. New insights into the electrochemical hydrogen oxidation and evolution reaction mechanism. Energy Environ. Sci. 7, 2255–2260 (2014).

    Article  Google Scholar 

  20. 20

    Zheng, Y., Jiao, Y. & Qiao, S. Z. Engineering of carbon-based electrocatalysts for emerging energy conversion: from fundamentality to functionality. Adv. Mater. 27, 5372–5378 (2015).

    Article  Google Scholar 

  21. 21

    Zhang, J., Zhao, Z., Xia, Z. & Dai, L. M. A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions. Nat. Nanotech. 10, 444–452 (2015).

    Article  Google Scholar 

  22. 22

    Zhao, Z., Li, M., Zhang, L., Dai, L. & Xia, Z. Design principles for heteroatom-doped carbon nanomaterials as highly efficient catalysts for fuel cells and metal–air batteries. Adv. Mater. 27, 6834–6840 (2015).

    Article  Google Scholar 

  23. 23

    Zhao, Y., Nakamura, R., Kamiya, K., Nakanishi, S. & Hashimoto, K. Nitrogen-doped carbon nanomaterials as non-metal electrocatalysts for water oxidation. Nat. Commun. 4, 2390 (2013).

    Article  Google Scholar 

  24. 24

    Zheng, Y. et al. Toward design of synergistically active carbon-based catalysts for electrocatalytic hydrogen evolution. ACS Nano 8, 5290–5296 (2014).

    Article  Google Scholar 

  25. 25

    McCrory, C. C. L. et al. Benchmarking hydrogen evolving reaction and oxygen evolving reaction electrocatalysts for solar water splitting devices. J. Am. Chem. Soc. 137, 4347–4357 (2015).

    Article  Google Scholar 

  26. 26

    Wang, D.-W. & Su, D. Heterogeneous nanocarbon materials for oxygen reduction reaction. Energy Environ. Sci. 7, 576–591 (2014).

    Article  Google Scholar 

  27. 27

    Paraknowitsch, J. P. & Thomas, A. Doping carbons beyond nitrogen: an overview of advanced heteroatom doped carbons with boron, sulphur and phosphorus for energy applications. Energy Environ. Sci. 6, 2839–2855 (2013).

    Article  Google Scholar 

  28. 28

    Lehmann, J. et al. in Biophysico-Chemical Processes Involving Natural Nonliving Organic Matter in Environmental Systems 729–781 (John Wiley, 2009).

    Google Scholar 

  29. 29

    Conway, B. E. & Tilak, B. V. Interfacial processes involving electrocatalytic evolution and oxidation of H2, and the role of chemisorbed H. Electrochim. Acta 47, 3571–3594 (2002).

    Article  Google Scholar 

  30. 30

    Li, Y. et al. MoS2 nanoparticles grown on graphene: an advanced catalyst for the hydrogen evolution reaction. J. Am. Chem. Soc. 133, 7296–7299 (2011).

    Article  Google Scholar 

  31. 31

    Jaramillo, T. F. et al. Identification of active edge sites for electrochemical H2 evolution from MoS2 nanocatalysts. Science 317, 100–102 (2007).

    Article  Google Scholar 

  32. 32

    Hammer, B. & Nørskov, J. K. in Advances in Catalysis Vol. 45, 71–129 (Academic, 2000).

    Google Scholar 

  33. 33

    Zheng, Y., Jiao, Y., Ge, L., Jaroniec, M. & Qiao, S. Z. Two-step boron and nitrogen doping in graphene for enhanced synergistic catalysis. Angew. Chem. Int. Ed. 52, 3110–3116 (2013).

    Article  Google Scholar 

  34. 34

    Liang, J., Jiao, Y., Jaroniec, M. & Qiao, S. Z. Sulfur and nitrogen dual-doped mesoporous graphene electrocatalyst for oxygen reduction with synergistically enhanced performance. Angew. Chem. Int. Ed. 51, 11496–11500 (2012).

    Article  Google Scholar 

  35. 35

    Qu, K., Zheng, Y., Dai, S. & Qiao, S. Z. Graphene oxide-polydopamine derived N, S-codoped carbon nanosheets as superior bifunctional electrocatalysts for oxygen reduction and evolution. Nano Energy 19, 373–381 (2016).

    Article  Google Scholar 

  36. 36

    Kibsgaard, J., Chen, Z., Reinecke, B. N. & Jaramillo, T. F. Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis. Nat. Mater. 11, 963–969 (2012).

    Article  Google Scholar 

  37. 37

    Liang, H. W. et al. Molecular metal-Nx centres in porous carbon for electrocatalytic hydrogen evolution. Nat. Commun. 6, 7992 (2015).

    Article  Google Scholar 

  38. 38

    Geng, D. & Sun, X. in Nanocarbons for Advanced Energy Conversion 17–42 (Wiley, 2015).

    Google Scholar 

  39. 39

    Lin, T. et al. Nitrogen-doped mesoporous carbon of extraordinary capacitance for electrochemical energy storage. Science 350, 1508–1513 (2015).

    Article  Google Scholar 

  40. 40

    Yeom, D.-Y. et al. High-concentration boron doping of graphene nanoplatelets by simple thermal annealing and their supercapacitive properties. Sci. Rep. 5, 9817 (2015).

    Article  Google Scholar 

  41. 41

    Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558–561 (1993).

    Article  Google Scholar 

  42. 42

    Kresse, G. & Hafner, J. Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium. Phys. Rev. B 49, 14251–14269 (1994).

    Article  Google Scholar 

  43. 43

    Kresse, G. & Furthmüller, 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).

    Article  Google Scholar 

  44. 44

    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 

  45. 45

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

    Article  Google Scholar 

  46. 46

    Perdew, J. P., Burke, K. & Ernzerhof, M. ERRATA Generalized gradient approximation made simple. Phys. Rev. Lett. 78, 1396 (1997).

    Article  Google Scholar 

  47. 47

    Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).

    Article  Google Scholar 

  48. 48

    Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).

    Article  Google Scholar 

  49. 49

    Bard, A. J. & Faulkner, L. R. Electrochemical Methods: Fundamentals and Applications (Wiley, 2000).

    Google Scholar 

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This research was supported by the Australian Research Council Discovery Projects (DP160104866, DP140104062, DP130104459 and DE160101163). NEXAFS measurements were undertaken on the soft X-ray beamline at the Australian Synchrotron. DFT calculations were undertaken at the NCI National Facility systems at the Australian National University through the National Computational Merit Allocation Scheme supported by the Australian Government.

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Y.J., Y.Z. and S.-Z.Q. conceived the project. Y.J. performed the DFT computations. Y.Z. synthesized the catalysts and conducted electrochemical measurements. Y.J. and Y.Z. analysed the data. All authors co-wrote the manuscript.

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Correspondence to Shi-Zhang Qiao.

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The authors declare no competing financial interests.

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Supplementary Figures 1–15, Supplementary Table 1, Supplementary Note 1–5, Supplementary References. (PDF 2057 kb)

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Jiao, Y., Zheng, Y., Davey, K. et al. Activity origin and catalyst design principles for electrocatalytic hydrogen evolution on heteroatom-doped graphene. Nat Energy 1, 16130 (2016).

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