A universal principle for a rational design of single-atom electrocatalysts

  • A Correction to this article was published on 20 July 2018


Developing highly active single-atom catalysts for electrochemical reactions is a key to future renewable energy technology. Here we present a universal design principle to evaluate the activity of graphene-based single-atom catalysts towards the oxygen reduction, oxygen evolution and hydrogen evolution reactions. Our results indicate that the catalytic activity of single-atom catalysts is highly correlated with the local environment of the metal centre, namely its coordination number and electronegativity and the electronegativity of the nearest neighbour atoms, validated by available experimental data. More importantly, we reveal that this design principle can be extended to metal–macrocycle complexes. The principle not only offers a strategy to design highly active nonprecious metal single-atom catalysts with specific active centres, for example, Fe-pyridine/pyrrole-N4 for the oxygen reduction reaction; Co-pyrrole-N4 for the oxygen evolution reaction; and Mn-pyrrole-N4 for the hydrogen evolution reaction to replace precious Pt/Ir/Ru-based catalysts, but also suggests that macrocyclic metal complexes could be used as an alternative to graphene-based single-atom catalysts.

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Fig. 1: Schematic of a single TM atom supported on graphene with different coordination environments.
Fig. 2: Adsorption free energies of adsorbates and electrocatalytic activity as a function of ΔGOH* and ΔGH*.
Fig. 3: ΔGOH*, ΔGH* and electrocatalytic activity as a function of descriptor φ.
Fig. 4: Extension of descriptor φ to SAC-like metal–macrocycle complexes.

Change history

  • 20 July 2018

    The original Supplementary Information file published with this Article was an older version; it was missing several Tables, and the Methods section was a duplicate of that from the main article. A new Supplementary Information file has been uploaded with these issues corrected.


  1. 1.

    Luo, J. et al. Water photolysis at 12.3% efficiency via perovskite photovoltaics and Earth-abundant catalysts. Science 345, 1593–1596 (2014).

    Article  CAS  PubMed  Google Scholar 

  2. 2.

    Chen, C. et al. Highly crystalline multimetallic nanoframes with three-dimensional electrocatalytic surfaces. Science 343, 1339–1343 (2014).

    Article  CAS  PubMed  Google Scholar 

  3. 3.

    Wang, Y. J. et al. Carbon-supported Pt-based alloy electrocatalysts for the oxygen reduction reaction in polymer electrolyte membrane fuel cells: particle size, shape, and composition manipulation and their impact to activity. Chem. Rev. 115, 3433–3467 (2015).

    Article  CAS  PubMed  Google Scholar 

  4. 4.

    Holewinski, A., Idrobo, J. C. & Linic, S. High-performance Ag–Co alloy catalysts for electrochemical oxygen reduction. Nat. Chem. 6, 828–834 (2014).

    Article  CAS  PubMed  Google Scholar 

  5. 5.

    Bai, X. et al. Theoretical investigation on the reaction pathways for oxygen reduction reaction on silicon doped graphene as potential metal-free catalyst. J. Electrochem. Soc. 163, F1496–F1502 (2016).

    Article  CAS  Google Scholar 

  6. 6.

    Greeley, J. et al. Alloys of platinum and early transition metals as oxygen reduction electrocatalysts. Nat. Chem. 1, 552–556 (2009).

    Article  CAS  PubMed  Google Scholar 

  7. 7.

    Yang, X.-F. et al. Single-atom catalysts: a new frontier in heterogeneous catalysis. Acc. Chem. Res. 46, 1740–1748 (2013).

    Article  CAS  PubMed  Google Scholar 

  8. 8.

    Qiao, B. et al. Single-atom catalysis of CO oxidation using Pt1/FeOx. Nat. Chem. 3, 634–641 (2011).

    Article  CAS  PubMed  Google Scholar 

  9. 9.

    Wu, G., More, K. L., Johnston, C. M. & Zelenay, P. High-performance electrocatalysts for oxygen reduction derived from polyaniline, iron, and cobalt. Science 332, 443–447 (2011).

    Article  CAS  PubMed  Google Scholar 

  10. 10.

    Lefèvre, M., Proietti, E., Jaouen, F. & Dodelet, J. P. Iron-based catalysts with improved oxygen reduction activity in polymer electrolyte fuel cells. Science 324, 71–74 (2009).

    Article  CAS  PubMed  Google Scholar 

  11. 11.

    Fei, H. et al. Atomic cobalt on nitrogen-doped graphene for hydrogen generation. Nat. Commun. 6, 8668 (2015).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  12. 12.

    Fan, L. et al. Atomically isolated nickel species anchored on graphitized carbon for efficient hydrogen evolution electrocatalysis. Nat. Commun. 7, 10667 (2016).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  13. 13.

    Chen, Y. et al. Isolated single iron atoms anchored on N-doped porous carbon as an efficient electrocatalyst for the oxygen reduction reaction. Angew. Chem. Int. Ed. 56, 6937–6941 (2017).

    Article  CAS  Google Scholar 

  14. 14.

    Zhang, X. et al. Catalytically active single-atom niobium in graphitic layers. Nat. Commun. 4, 1924 (2013).

    Article  CAS  PubMed  Google Scholar 

  15. 15.

    Chen, W. et al. Rational design of single molybdenum atoms anchored on N-doped carbon for effective hydrogen evolution reaction. Angew. Chem. Int. Ed. 56, 16086–16090 (2017).

    Article  CAS  Google Scholar 

  16. 16.

    Chen, X., Chen, S. & Wang, J. Screening of catalytic oxygen reduction reaction activity of metal-doped graphene by density functional theory. Appl. Surf. Sci. 379, 291–295 (2016).

    Article  CAS  Google Scholar 

  17. 17.

    Li, X., Zhong, W., Peng, C., Li, J. & Jiang, J. Design of efficient catalysts with double transition metal atoms on C2N layer. J. Phys. Chem. Lett. 7, 1750–1755 (2016).

    Article  CAS  PubMed  Google Scholar 

  18. 18.

    Zagal, J. H., Griveau, S., Silva, J. F., Nyokong, T. & Bedioui, F. Metallophthalocyanine-based molecular materials as catalysts for electrochemical reactions. Coord. Chem. Rev. 254, 2755–2791 (2010).

    Article  CAS  Google Scholar 

  19. 19.

    Costentin, C. & Savéant, J.-M. Towards an intelligent design of molecular electrocatalysts. Nat. Rev. Chem. 1, 0087 (2017).

    Article  CAS  Google Scholar 

  20. 20.

    Zitolo, A. et al. Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials. Nat. Mater. 14, 937–942 (2015).

    Article  CAS  PubMed  Google Scholar 

  21. 21.

    Liu, W. et al. Single-atom dispersed Co-N-C catalyst: structure identification and performance for hydrogenative coupling of nitroarenes. Chem. Sci. 7, 5758–5764 (2016).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  22. 22.

    Kramm, U. I. et al. On an easy way to prepare metal–nitrogen doped carbon with exclusive presence of MeN4-type sites active for the ORR. J. Am. Chem. Soc. 138, 635–640 (2015).

    Article  CAS  Google Scholar 

  23. 23.

    Sahraie, N. R. et al. Quantifying the density and utilization of active sites in non-precious metal oxygen electroreduction catalysts. Nat. Commun. 6, 8618–8626 (2015).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  24. 24.

    Greeley, J., Jaramillo, T. F., Bonde, J., Chorkendorff, I. B. & Nørskov, J. K. Computational high-throughput screening of electrocatalytic materials for hydrogen evolution. Nat. Mater. 5, 909–913 (2006).

    Article  CAS  PubMed  Google Scholar 

  25. 25.

    Stamenkovic, V. R. et al. Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces. Nat. Mater. 6, 241–247 (2007).

    Article  CAS  PubMed  Google Scholar 

  26. 26.

    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  CAS  PubMed  PubMed Central  Google Scholar 

  27. 27.

    Suntivich, J., Gasteiger, H., Yabuuchi, N., Goodenough, J. B. & Shao-Horn, Y. Design principles for oxygen reduction activity on perovskite oxides in alkaline environment. Nat. Chem. 3, 546–550 (2011).

    Article  CAS  PubMed  Google Scholar 

  28. 28.

    Tao, H. B. et al. Identification of surface reactivity descriptor for transition metal oxides in oxygen evolution reaction. J. Am. Chem. Soc. 138, 9978–9985 (2016).

    Article  CAS  PubMed  Google Scholar 

  29. 29.

    Calle-Vallejo, F., Loffreda, D., Koper, M. T. M. & Sautet, P. Introducing structural sensitivity into adsorption-energy scaling relations by means of coordination numbers. Nat. Chem. 7, 403–410 (2015).

    Article  CAS  PubMed  Google Scholar 

  30. 30.

    Chung, H. T. et al. Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst. Science 357, 479–484 (2017).

    Article  CAS  PubMed  Google Scholar 

  31. 31.

    Liu, J. et al. High-performance oxygen reduction electrocatalysts based on cheap carbon black, nitrogen, and trace iron. Adv. Mater. 25, 6879–6883 (2013).

    Article  CAS  PubMed  Google Scholar 

  32. 32.

    Liu, J. et al. High performance platinum single atom electrocatalyst for oxygen reduction reaction. Nat. Commun. 8, 15938 (2017).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  33. 33.

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

    Article  CAS  Google Scholar 

  34. 34.

    Koper, M. T. M. Thermodynamic theory of multi-electron transfer reactions: implications for electrocatalysis. J. Electroanal. Chem. 660, 254–260 (2011).

    Article  CAS  Google Scholar 

  35. 35.

    Rossmeisl, J., Qu, Z. W., Zhu, H., Kroes, G. J. & Nørskov, J. K. Electrolysis of water on oxide surfaces. J. Electroanal. Chem. 607, 83–89 (2007).

    Article  CAS  Google Scholar 

  36. 36.

    Kaukonen, M., Krasheninnikov, A. V., Kauppinen, E. & Nieminen, R. M. Doped graphene as a material for oxygen reduction reaction in hydrogen fuel cells: a computational study. ACS Catal. 3, 159–165 (2013).

    Article  CAS  Google Scholar 

  37. 37.

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

    Article  CAS  Google Scholar 

  38. 38.

    Hong, W. T. et al. Toward the rational design of non-precious transition metal oxides for oxygen electrocatalysis. Energy Environ. Sci. 8, 1404–1427 (2015).

    Article  CAS  Google Scholar 

  39. 39.

    Bligaard, T. & Nørskov, J. K. Chemical Bonding at Surfaces and Interfaces 257–278 (Elsevier, Amsterdam, 2008).

  40. 40.

    Yin, P. et al. Single cobalt atoms with precise N-coordination as superior oxygen reduction reaction catalysts. Angew. Chem. Int. Ed. 55, 10800–10805 (2016).

    Article  CAS  Google Scholar 

  41. 41.

    Wang, Z.-L. et al. C and N hybrid coordination derived Co–C–N complex as a highly efficient electrocatalyst for hydrogen evolution reaction. J. Am. Chem. Soc. 137, 15070–15073 (2015).

    Article  CAS  PubMed  Google Scholar 

  42. 42.

    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 (2015).

    Article  CAS  Google Scholar 

  43. 43.

    Jiang, S., Zhu, C. & Dong, S. Cobalt and nitrogen-cofunctionalized graphene as a durable non-precious metal catalyst with enhanced ORR activity. J. Mater. Chem. A 1, 3593–3599 (2013).

    Article  CAS  Google Scholar 

  44. 44.

    Liu, X., Amiinu, I. S., Liu, S., Cheng, K. & Mu, S. Transition metal/nitrogen dual-doped mesoporous graphene-like carbon nanosheets for the oxygen reduction and evolution reactions. Nanoscale 8, 13311–13320 (2016).

    Article  CAS  PubMed  Google Scholar 

  45. 45.

    Hou, Y. et al. An advanced nitrogen-doped graphene/cobalt-embedded porous carbon polyhedron hybrid for efficient catalysis of oxygen reduction and water splitting. Adv. Funct. Mater. 25, 872–882 (2015).

    Article  CAS  Google Scholar 

  46. 46.

    Morozan, A., Goellner, V., Nedellec, Y., Hannauer, J. & Jaouen, F. Effect of the transition metal on metal–nitrogen–carbon catalysts for the hydrogen evolution reaction. J. Electrochem. Soc. 162, H719–H726 (2015).

    Article  CAS  Google Scholar 

  47. 47.

    Baran, J. D., Grönbeck, H. & Hellman, A. Analysis of porphyrines as catalysts for electrochemical reduction of O2 and oxidation of H2O. J. Am. Chem. Soc. 136, 1320–1326 (2014).

    Article  CAS  PubMed  Google Scholar 

  48. 48.

    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  CAS  PubMed  Google Scholar 

  49. 49.

    Abel, M., Clair, S., Ourdjini, O., Mossoyan, M. & Porte, L. Single layer of polymeric Fe-phthalocyanine: an organometallic sheet on metal and thin insulating film. J. Am. Chem. Soc. 133, 1203–1205 (2011).

    Article  CAS  PubMed  Google Scholar 

  50. 50.

    Stepanow, S. et al. Spin tuning of electron-doped metal–phthalocyanine layers. J. Am. Chem. Soc. 136, 5451–5459 (2014).

    Article  CAS  PubMed  Google Scholar 

  51. 51.

    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  CAS  Google Scholar 

  52. 52.

    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).

    Article  CAS  Google Scholar 

  53. 53.

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

    Article  CAS  Google Scholar 

  54. 54.

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

    Article  CAS  Google Scholar 

  55. 55.

    Dudarev, S. L., Botton, G. A., Savrasov, S. Y., Humphreys, C. J. & Sutton, A. P. Electron-energy-loss spectra and the structural stability of nickel oxide: an LSDA + U study. Phys. Rev. B 57, 1505–1509 (1998).

    Article  CAS  Google Scholar 

  56. 56.

    Mathew, K., Sundararaman, R., Letchworthweaver, K., Arias, T. A. & Hennig, R. G. Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways. J. Chem. Phys. 140, 084106 (2014).

    Article  CAS  PubMed  Google Scholar 

  57. 57.

    Calle-Vallejo, F., Martínez, J. I., García-Lastra, J. M., Abad, E. & Koper, M. T. M. Oxygen reduction and evolution at single-metal active sites: Comparison between functionalized graphitic materials and protoporphyrins. Surf. Sci. 607, 47–53 (2013).

    Article  CAS  Google Scholar 

  58. 58.

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

    Article  CAS  Google Scholar 

  59. 59.

    Desai, S. K. & Neurock, M. First-principles study of the role of solvent in the dissociation of water over a Pt-Ru alloy. Phys. Rev. B 68, 1071–1086 (2003).

    Article  CAS  Google Scholar 

  60. 60.

    Rossmeisl, J., Logadottir, A. & Nørskov, J. K. Electrolysis of water on (oxidized) metal surfaces. Chem. Phys. 319, 178–184 (2005).

    Article  CAS  Google Scholar 

  61. 61.

    De Paula, J. Atkins’ Physical Chemistry (Oxford University Press, Oxford, 2010).

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This work is supported by the National Natural Science Foundation of China (91634116, 21576008, 21625601).

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D.J.C. and X.C.Z. conceived the original idea and designed the DFT calculations. D.J.C. and H.X. contributed to the density functional theory calculations. D.P.C. analysed the results. All authors wrote the manuscript and have reviewed, discussed and approved the results and conclusions of this article.

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Correspondence to Daojian Cheng or Dapeng Cao or Xiao Cheng Zeng.

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Xu, H., Cheng, D., Cao, D. et al. A universal principle for a rational design of single-atom electrocatalysts. Nat Catal 1, 339–348 (2018). https://doi.org/10.1038/s41929-018-0063-z

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