Multi-site electrocatalysts for hydrogen evolution in neutral media by destabilization of water molecules

Abstract

High-performance hydrogen evolution reaction (HER) catalysts are compelling for the conversion of renewable electricity to fuels and feedstocks. The best HER catalysts rely on the use of platinum and show the highest performance in acidic media. Efficient HER catalysts based on inexpensive and Earth-abundant elements that operate in neutral (hence biocompatible) media could enable low-cost direct seawater splitting and the realization of bio-upgraded chemical fuels. In the challenging neutral-pH environment, water splitting is a multistep reaction. Here we present a HER catalyst comprising Ni and CrOx sites doped onto a Cu surface that operates efficiently in neutral media. The Ni and CrOx sites have strong binding energies for hydrogen and hydroxyl groups, respectively, which accelerates water dissociation, whereas the Cu has a weak hydrogen binding energy, promoting hydride coupling. The resulting catalyst exhibits a 48 mV overpotential at a current density of 10 mA cm−2 in a pH 7 buffer electrolyte. These findings suggest design principles for inexpensive, efficient and biocompatible catalytic systems.

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Fig. 1: Catalyst design principle and HER activities of CrOx/Cu–Ni catalysts.
Fig. 2: CrOx/Cu–Ni catalyst fine structures revealed by X-ray absorption spectroscopies.
Fig. 3: Ambient pressure XPS experiments of water adsorption on CrOx/Cu–Ni.
Fig. 4: Theoretical calculation of HER activation energy on CrOx/Cu–Ni catalysts.
Fig. 5: Design and characterization of the 3D CrOx/Cu–Ni catalyst.
Fig. 6: Electrochemical characterization of CrOx/Cu–Ni on 3D Cu foam.

Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

This work was supported by the Ontario Research Fund: Research Excellence Program, the Natural Sciences and Engineering Research Council (NSERC) of Canada, and the Connaught Global Challenge programme of the University of Toronto. F.P.G.d.A. acknowledges financial support from the Connaught Fund. P.D.L acknowledges financial support from NSERC in the form of the Canada Graduate Scholarship – Doctoral (CGS-D) award. This research used resources of the Advanced Light Source, which is a DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. This research also used resources of the Advanced Photon Source, an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science by Argonne National Laboratory and was supported by the US DOE under contract no. DE-AC02-06CH11357, and the Canadian Light Source and its funding partners. All DFT computations were performed on the IBM BlueGene/Q supercomputer with support from the Southern Ontario Smart Computing Innovation Platform (SOSCIP). SOSCIP is funded by the Federal Economic Development Agency of Southern Ontario, the Province of Ontario, IBM Canada Ltd., Ontario Centres of Excellence, Mitacs, and 15 Ontario academic member institutions.

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E.H.S. supervised the project. C.-T.D. and F.P.G.d.A. designed and carried out the experiments. A.J. carried out the DFT calculation. J.C., B.Z.G. and E.J.C. performed the AP-XPS measurements. J.L. performed the XAS measurements. C.-T.D., A.J., F.P.G.d.A. and E.H.S. wrote the manuscript. All the authors discussed the results and assisted during the manuscript preparation.

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Correspondence to Edward H. Sargent.

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Supplementary Figures 1–11, Supplementary Tables 1–3, Supplementary References

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Dinh, C., Jain, A., de Arquer, F.P.G. et al. Multi-site electrocatalysts for hydrogen evolution in neutral media by destabilization of water molecules. Nat Energy 4, 107–114 (2019). https://doi.org/10.1038/s41560-018-0296-8

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