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

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

Abstract

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.

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Acknowledgements

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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