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The role of adsorbed hydroxide in hydrogen evolution reaction kinetics on modified platinum

Nature Energy volume 5, pages 891–899 (2020)Cite this article

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Abstract

The bifunctional mechanism that involves adsorbed hydroxide in the alkaline hydrogen oxidation and evolution reactions, important in hydrogen fuel cells and water electrolysers, is hotly debated. Hydroxide binding has been suggested to impact activity, but the exact role of adsorbed hydroxide in the reaction mechanism is unknown. Here, by selectively decorating steps on a Pt single crystal with other metal atoms, we show that the rate of alkaline hydrogen evolution exhibits a volcano-type relationship with the hydroxide binding strength. We find that Pt decorated with Ru at the step edge is 65 times more active for the hydrogen evolution reaction (HER) than is the bare Pt step. Simulations of electrochemical water dissociation show that the activation energy correlates with the OH* adsorption strength, even when the adsorbed hydroxide is not a product, which leads to a simulated volcano curve that matches the experimental curve. This work not only illustrates the alkaline HER mechanism but also provides a goal for catalyst design in targeting an optimum hydroxide binding strength to yield the highest rate for the alkaline HER. A three-dimensional (H and OH adsorbed species) HER activity volcano and the implications for hydrogen oxidation are discussed.

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Fig. 1: Step-decoration procedure, voltammetry and HER activity.
Fig. 2: Experimentally measured HER activity on step-decorated Pt(553).
Fig. 3: DFT-simulated activation energy of water dissociation (the alkaline Volmer reaction).
Fig. 4: Simulated and experimentally measured HER activity and HER reaction mechanism.
Fig. 5: 3D HER activity volcano for catalyst design.

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Data availability

All the data are available in the main text and Supplementary Information. Additional datasets related to this study are available from the corresponding author upon reasonable request. Source data are provided with this paper.

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Acknowledgements

This project received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement no. 707404. The use of supercomputing facilities at SURFsara was sponsored by NWO Physical Sciences, with financial support by NWO.

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  1. Ian T. McCrum

    Present address: Department of Chemical & Biomolecular Engineering, Clarkson University, Potsdam, NY, USA

Authors and Affiliations

  1. Leiden Institute of Chemistry, Leiden University, Leiden, the Netherlands

    Ian T. McCrum & Marc T. M. Koper

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Contributions

I.T.M. and M.T.M.K. designed the experimental plan. I.T.M. carried out the experiments, DFT simulations and data analysis. I.T.M. and M.T.M.K. wrote the manuscript.

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Correspondence to Marc T. M. Koper.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–20, Notes 1 and 2, and Table 1.

Source data

Source Data Fig. 1

Experimentally measured data for voltammograms and HER activity shown in Fig. 1b,d.

Source Data Fig. 2

Experimentally measured HER activity and DFT-simulated hydroxide adsorption energy shown in Fig. 2.

Source Data Fig. 3

DFT-simulated chemical and electrochemical water dissociation barrier on decorated stepped surfaces shown in Fig. 3a. DFT-simulated H–OH bond length during reaction path shown in Fig. 3b. VASP CONTCAR (atomic structure) for image of transition state in Fig. 3c.

Source Data Fig. 4

Experimentally measured HER activity, DFT-calculated hydroxide adsorption free energy, and parameters used for DFT model of HER reaction rate shown in Fig. 4a.

Source Data Fig. 5

DFT-calculated hydrogen and hydroxide adsorption strengths plotted in Fig. 5.

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McCrum, I.T., Koper, M.T.M. The role of adsorbed hydroxide in hydrogen evolution reaction kinetics on modified platinum. Nat Energy 5, 891–899 (2020). https://doi.org/10.1038/s41560-020-00710-8

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