Hydrogen evolution by a metal-free electrocatalyst

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Abstract

Electrocatalytic reduction of water to molecular hydrogen via the hydrogen evolution reaction may provide a sustainable energy supply for the future, but its commercial application is hampered by the use of precious platinum catalysts. All alternatives to platinum thus far are based on nonprecious metals, and, to our knowledge, there is no report about a catalyst for electrocatalytic hydrogen evolution beyond metals. Here we couple graphitic-carbon nitride with nitrogen-doped graphene to produce a metal-free hybrid catalyst, which shows an unexpected hydrogen evolution reaction activity with comparable overpotential and Tafel slope to some of well-developed metallic catalysts. Experimental observations in combination with density functional theory calculations reveal that its unusual electrocatalytic properties originate from an intrinsic chemical and electronic coupling that synergistically promotes the proton adsorption and reduction kinetics.

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Figure 1: Electron microscopy characterization of C3N4@NG nanosheet.
Figure 2: Chemical structure of C3N4@NG.
Figure 3: DFT calculation studies of C3N4@NG.
Figure 4: Fundamental electrochemical relationships measured for HER on C3N4@NG.
Figure 5: DFT-calculated HER activities of C3N4@NG.
Figure 6: HER mechanism.

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Acknowledgements

This research is financially supported by Australian Research Council (DP1095861, DP130104459). NEXAFS measurements were undertaken on the soft X-ray beamline at Australian Synchrotron. DFT calculations were undertaken on the NCI National Facility systems through the National Computational Merit Allocation Scheme.

Author information

S.Z.Q. designed the research. Y.Z. synthesized catalysts and conducted chemical characterizations and electrochemical measurements. Y.J. performed the DFT calculations, assisted by A.D., Y.H.Z. and Y.H. carried out high-resolution transmission electron microscopy imaging. L.H.L. and Y.C. made NEXAFS measurements. All authors discussed and analysed the data. S.Z.Q., Y.Z., Y.J. co-wrote the manuscript with input from M.J. and Y.H.

Correspondence to Shi Zhang Qiao.

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The authors declare no competing financial interests.

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Supplementary Information

Supplementary Figures 1-11, Supplementary Tables 1-4, Supplementary Methods and Supplementary References (PDF 2339 kb)

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