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Hydride formation thermodynamics and hysteresis in individual Pd nanocrystals with different size and shape

Abstract

Physicochemical properties of nanoparticles may depend on their size and shape and are traditionally assessed in ensemble-level experiments, which accordingly may be plagued by averaging effects. These effects can be eliminated in single-nanoparticle experiments. Using plasmonic nanospectroscopy, we present a comprehensive study of hydride formation thermodynamics in individual Pd nanocrystals of different size and shape, and find corresponding enthalpies and entropies to be nearly size- and shape-independent. The hysteresis observed is significantly wider than in bulk, with details depending on the specifics of individual nanoparticles. Generally, the absorption branch of the hysteresis loop is size-dependent in the sub-30 nm regime, whereas desorption is size- and shape-independent. The former is consistent with a coherent phase transition during hydride formation, influenced kinetically by the specifics of nucleation, whereas the latter implies that hydride decomposition either occurs incoherently or via different kinetic pathways.

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Figure 1: Heterodimer arrangement of a plasmonic Au nanoantenna combined with a shape-selected Pd nanoparticle.
Figure 2: Experimental procedure and theoretical FDTD simulations.
Figure 3: p–Δλmax isotherms measured at four temperatures for Pd nanocubes.
Figure 4: Van’t Hoff analysis.
Figure 5: pλmax isotherms measured at four temperatures for Pd nanoparticles of different shape.
Figure 6: Summary of the size and shape dependence of hydride formation thermodynamics and hysteresis.

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Acknowledgements

We acknowledge financial support from the Swedish Research Council (C.L.), the Chalmers Areas of Advance Nano (S.S., C.L., Y.A.D.F., K.M.-P., F.W.) and Materials Science (K.M.-P.), the Swedish Foundation for Strategic Research Framework Program RMA11–0037 (C.W., F.A.A.N., C.L.), the Polish National Science Center via the project 2012/07/D/ST3/02152 (D.Ś. and T.J.A.) and the ERC-StG 337221 ‘SIMONE’ (K.M.-P.). We gratefully acknowledge S. Gustafsson for help with high-resolution TEM imaging of the Pd nanorods. C.L. and S.S. acknowledge valuable discussions with R. Griessen and I. Zorić.

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S.S. and C.L. planned the experiments, analysed the data, and wrote the paper. S.S. performed the single-particle measurements. C.W. and F.A.A.N. executed the ensemble measurements and XPS analysis. T.A.G., Y.A.D.F., G.N., F.W. and K.M.-P. synthesized and self-assembled the nanoparticle heterodimers. T.J.A. and D.Ś. performed the FDTD simulations. V.P.Z. contributed the theoretical analysis of lattice strain and dislocation formation. C.L. conceived the general approach and coordinated the project.

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Correspondence to Christoph Langhammer.

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Syrenova, S., Wadell, C., Nugroho, F. et al. Hydride formation thermodynamics and hysteresis in individual Pd nanocrystals with different size and shape. Nature Mater 14, 1236–1244 (2015). https://doi.org/10.1038/nmat4409

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