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In situ detection of hydrogen-induced phase transitions in individual palladium nanocrystals

Abstract

Many energy- and information-storage processes rely on phase changes of nanomaterials in reactive environments. Compared to their bulk counterparts, nanostructured materials seem to exhibit faster charging and discharging kinetics, extended life cycles, and size-tunable thermodynamics. However, in ensemble studies of these materials, it is often difficult to discriminate between intrinsic size-dependent properties and effects due to sample size and shape dispersity. Here, we detect the phase transitions of individual palladium nanocrystals during hydrogen absorption and desorption, using in situ electron energy-loss spectroscopy in an environmental transmission electron microscope. In contrast to ensemble measurements, we find that palladium nanocrystals undergo sharp transitions between the α and β phases, and that surface effects dictate the size dependence of the hydrogen absorption pressures. Our results provide a general framework for monitoring phase transitions in individual nanocrystals in a reactive environment and highlight the importance of single-particle approaches for the characterization of nanostructured materials.

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Figure 1: Pd nanocube TEM and in situ EELS set-up.
Figure 2: EEL spectra of a single Pd nanocrystal at varying H2 pressures.
Figure 3: Single-particle isotherms.
Figure 4: Surface stress effect on the loading equilibrium pressures.

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Acknowledgements

We gratefully acknowledge scientific feedback and discussions with J. Scholl, W. D. Nix, R. Griessen and A. Pundt. J.A.D. acknowledges support from a Stanford Terman Fellowship, a Hellman Fellowship, an Air Force Office of Scientific Research Young Investigator Grant (FA9550-11-1-0024) and a National Science Foundation CAREER Award (DMR-1151231). This work was supported in part by a SLAC National Accelerator Laboratory LDRD award in concert with the Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, under contract DEAC02-76SF00515. Work was also supported by the Young Energy Scientist (YES!) Fellowship of the Foundation for Fundamental Research on Matter (FOM), which is financially supported by the Netherlands Organisation for Scientific Research (NWO), and by an award from the Department of Energy (DOE) Office of Science Graduate Fellowship Program administered by the Oak Ridge Institute for Science and Education for the DOE. ORISE is managed by Oak Ridge Associated Universities (ORAU) under DOE contract number DE-AC05-06OR23100. All opinions expressed in this paper are of the authors and do not necessarily reflect the policies and views of NSF, DOE, ORAU or ORISE.

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A.B., T.C.N. and J.A.D. designed the experiments and A.B., T.C.N. and A.L.K. performed the experiments. A.B. and T.C.N. analysed the data and wrote the initial draft of the manuscript. J.A.D. supervised the project, and all authors discussed the results and contributed to final manuscript preparation.

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Correspondence to Andrea Baldi, Tarun C. Narayan or Jennifer A. Dionne.

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Baldi, A., Narayan, T., Koh, A. et al. In situ detection of hydrogen-induced phase transitions in individual palladium nanocrystals. Nature Mater 13, 1143–1148 (2014). https://doi.org/10.1038/nmat4086

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