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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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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.

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All the data that support the findings of this study are available from the corresponding author upon reasonable request.

References

  1. Calle-Vallejo, F., Loffreda, D., Koper, M. T. M. & Sautet, P. Introducing structural sensitivity into adsorption—energy scaling relations by means of coordination numbers. Nat. Chem. 7, 403–410 (2015).

    Article  CAS  Google Scholar 

  2. Lee, I., Delbecq, F., Morales, R., Albiter, M. A. & Zaera, F. Tuning selectivity in catalysis by controlling particle shape. Nat. Mater. 8, 132–138 (2009).

    Article  CAS  Google Scholar 

  3. Teschner, D. et al. The roles of subsurface carbon and hydrogen in palladium-catalyzed alkyne hydrogenation. Science 320, 86–89 (2008).

    Article  CAS  Google Scholar 

  4. Li, G. et al. Hydrogen storage in Pd nanocrystals covered with a metal–organic framework. Nat. Mater. 13, 802–806 (2014).

    Article  CAS  Google Scholar 

  5. Liu, N., Tang, M. L., Hentschel, M., Giessen, H. & Alivisatos, A. P. Nanoantenna-enhanced gas sensing in a single tailored nanofocus. Nat. Mater. 10, 631–636 (2011).

    Article  CAS  Google Scholar 

  6. Bardhan, R. et al. Uncovering the intrinsic size dependence of hydriding phase transformations in nanocrystals. Nat. Mater. 12, 905–912 (2013).

    Article  CAS  Google Scholar 

  7. Syrenova, S. et al. Hydride formation thermodynamics and hysteresis in individual Pd nanocrystals with different size and shape. Nat. Mater. 14, 1236–1244 (2015).

    Article  CAS  Google Scholar 

  8. Griessen, R., Strohfeldt, N. & Giessen, H. Thermodynamics of the hybrid interaction of hydrogen with palladium nanoparticles. Nat. Mater. 15, 311–317 (2016).

    Article  CAS  Google Scholar 

  9. Ulvestad, A. et al. Avalanching strain dynamics during the hydriding phase transformation in individual palladium nanoparticles. Nat. Commun. 6, 10092 (2015).

    Article  CAS  Google Scholar 

  10. Narayan, T. C. et al. Direct visualization of hydrogen absorption dynamics in individual palladium nanoparticles. Nat. Commun. 8, 14020 (2017).

    Article  CAS  Google Scholar 

  11. Narayan, T. C., Baldi, A., Koh, A. L., Sinclair, R. & Dionne, J. A. Reconstructing solute-induced phase transformations within individual nanocrystals. Nat. Mater. 15, 768–774 (2016).

    Article  CAS  Google Scholar 

  12. Wicke, E, Brodowsky, H. & Züchner, H. in Hydrogen in Metals II 73–155 (Springer, 1978).

  13. Baldi, A., Narayan, T. C., Koh, A. L. & Dionne, J. A. In situ detection of hydrogen-induced phase transitions in individual palladium nanocrystals. Nat. Mater. 13, 1143–1148 (2014).

    Article  CAS  Google Scholar 

  14. Ulvestad, A. et al. Three-dimensional imaging of dislocation dynamics during the hydriding phase transformation. Nat. Mater. 16, 565–571 (2017).

    Article  CAS  Google Scholar 

  15. Klinkova, A. et al. Shape-dependent interactions of palladium nanocrystals with hydrogen. Small 12, 2450–2458 (2016).

    Article  CAS  Google Scholar 

  16. Lim, B. et al. Shape-controlled synthesis of Pd nanocrystals in aqueous solutions. Adv. Funct. Mater. 19, 189–200 (2009).

    Article  CAS  Google Scholar 

  17. Sytwu, K. et al. Visualizing facet-dependent hydrogenation dynamics in individual palladium nanoparticles. Nano Lett. 9, 5357–5363 (2018).

    Article  Google Scholar 

  18. Li, G. et al. Shape-dependent hydrogen-storage properties in Pd nanocrystals: which does hydrogen prefer, octahedron (111) or cube (100)? J. Am. Chem. Soc. 136, 10222–10225 (2014).

    Article  CAS  Google Scholar 

  19. Zalineeva, A., Baranton, S., Coutanceau, C. & Jerkiewicz, G. Octahedral palladium nanoparticles as excellent hosts for electrochemically adsorbed and absorbed hydrogen. Sci. Adv. 3, e1600542 (2017).

    Article  Google Scholar 

  20. Sherbo, R. S. et al. Accurate coulometric quantification of hydrogen absorption in palladium nanoparticles and thin films. Chem. Mater. 30, 3963–3970 (2018).

    Article  CAS  Google Scholar 

  21. Satterfield, C. N. Heterogeneous Catalysis in Practice (McGraw-Hill, 1980).

  22. Stern, A., Resnik, A. & Shaltiel, D. Thermal desorption spectra of the PdHx system in a powder form. J. Phys. F 14, 1625–1639 (1984).

    Article  CAS  Google Scholar 

  23. Savara, A., Ludwig, W. & Schauermann, S. Kinetic evidence for a non-Langmuir–Hinshelwood surface reaction: H/D exchange over Pd nanoparticles and Pd(111). ChemPhysChem 14, 1686–1695 (2013).

    Article  CAS  Google Scholar 

  24. Jewell, L. L. & Davis, B. H. Review of absorption and adsorption in the hydrogen–palladium system. Appl. Catal. A 310, 1–15 (2006).

    Article  CAS  Google Scholar 

  25. Shen, X. et al. Hydrogen diffusion into the subsurfaces of model metal catalysts from first principles. Phys. Chem. Chem. Phys. 19, 3557–3564 (2017).

    Article  CAS  Google Scholar 

  26. Kobayashi, H. et al. On the nature of strong hydrogen atom trapping inside Pd nanoparticles. J. Am. Chem. Soc. 130, 1828–1829 (2008).

    Article  CAS  Google Scholar 

  27. Crespo-Quesada, M. et al. UV–ozone cleaning of supported poly(vinylpyrrolidone)-stabilized palladium nanocubes: effect of stabilizer removal on morphology and catalytic behavior. Langmuir 27, 7909–7916 (2011).

    Article  CAS  Google Scholar 

  28. Aricò, A. S., Bruce, P., Scrosati, B., Tarascon, J.-M. & van Schalkwijk, W. Nanostructured materials for advanced energy conversion and storage devices. Nat. Mater. 4, 366–377 (2005).

    Article  Google Scholar 

  29. Huiberts, J. N. et al. Yttrium and lanthanum hydride films with switchable optical properties. Nature 380, 231–234 (1996).

    Article  CAS  Google Scholar 

  30. Sherbo, R. S., Delima, R. S., Chiykowski, V. A., MacLeod, B. P. & Berlinguette, C. P. Complete electron economy by pairing electrolysis with hydrogenation. Nat. Catal. 1, 501–507 (2018).

    Article  Google Scholar 

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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).

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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.

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Correspondence to Curtis P. Berlinguette.

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Supplementary Information

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

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Johnson, N.J.J., Lam, B., MacLeod, B.P. et al. Facets and vertices regulate hydrogen uptake and release in palladium nanocrystals. Nat. Mater. 18, 454–458 (2019). https://doi.org/10.1038/s41563-019-0308-5

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