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Facets and vertices regulate hydrogen uptake and release in palladium nanocrystals

Abstract

Crystal facets, vertices and edges govern the energy landscape of metal surfaces and thus the chemical interactions on the surface1,2. The facile absorption and desorption of hydrogen at a palladium surface provides a useful platform for defining how metal–solute interactions impact properties relevant to energy storage, catalysis and sensing3,4,5. Recent advances in in operando and in situ techniques have enabled the phase transitions of single palladium nanocrystals to be temporally and spatially tracked during hydrogen absorption6,7,8,9,10,11. We demonstrate herein that in situ X-ray diffraction can be used to track both hydrogen absorption and desorption in palladium nanocrystals. This ensemble measurement enabled us to delineate distinctive absorption and desorption mechanisms for nanocrystals containing exclusively (111) or (100) facets. We show that the rate of hydrogen absorption is higher for those nanocrystals containing a higher number of vertices, consistent with hydrogen absorption occurring quickly after β-phase nucleation at lattice-strained vertices9,10. Tracking hydrogen desorption revealed initial desorption rates to be nearly tenfold faster for samples with (100) facets, presumably due to the faster recombination of surface hydrogen atoms. These results inspired us to make nanocrystals with a high number of vertices and (100) facets, which were found to accommodate fast hydrogen uptake and release.

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Acknowledgements

The authors acknowledge financial support from the Canadian Natural Science and Engineering Council (RGPIN 337345-13), Canadian Foundation for Innovation (229288), Canadian Institute for Advanced Research (BSE-BERL-162173), Collaborative Research and Development Grant (CRD-502052-16), Canada Research Chairs and Google LLC. This work made use of the 4D LABS shared facilities supported by the Canada Foundation for Innovation (CFI), British Columbia Knowledge Development Fund (BCKDF), Western Economic Diversification Canada (WD) and Simon Fraser University (SFU).

Author information

N.J.J.J., B.L. and C.P.B. devised the concept. N.J.J.J. synthesized and characterized the nanocrystals. B.L. designed and performed in situ studies. B.P.M. performed statistical analysis of experimental data. R.S.S. and M.M.-G. performed electrochemical hydrogen loading experiments. D.K.F. provided experimental and technical advice. N.J.J.J., B.L. and C.P.B. wrote the manuscript with input from all authors. C.P.B. supervised the project.

Competing interests

The authors declare no competing interests.

Correspondence to Curtis P. Berlinguette.

Supplementary Information

  1. Supplementary Information

    Supplementary Figures 1–16, Supplementary Tables 1,2, Supplementary Discussion

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DOI

https://doi.org/10.1038/s41563-019-0308-5

Fig. 1: Palladium nanocrystals with distinctive facets.
Fig. 2: In situ XRD monitoring the hydrogen-induced phase transformation
Fig. 3: Hydrogen absorption and desorption in palladium nanocrystals.
Fig. 4: Hydrogen diffusion and recombination at (111) and (100) facets.