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

Abstract

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.

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Acknowledgements

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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Contributions

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.

Corresponding author

Correspondence to Shi-Zhang Qiao.

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The authors declare no competing financial interests.

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Supplementary Information

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). https://doi.org/10.1038/nenergy.2016.130

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