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Uncovering the intrinsic size dependence of hydriding phase transformations in nanocrystals

Nature Materials volume 12, pages 905–912 (2013)Cite this article

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Abstract

A quantitative understanding of nanocrystal phase transformations would enable more efficient energy conversion and catalysis, but has been hindered by difficulties in directly monitoring well-characterized nanoscale systems in reactive environments. We present a new in situ luminescence-based probe enabling direct quantification of nanocrystal phase transformations, applied here to the hydriding transformation of palladium nanocrystals. Our approach reveals the intrinsic kinetics and thermodynamics of nanocrystal phase transformations, eliminating complications of substrate strain, ligand effects and external signal transducers. Clear size-dependent trends emerge in nanocrystals long accepted to be bulk-like in behaviour. Statistical mechanical simulations show these trends to be a consequence of nanoconfinement of a thermally driven, first-order phase transition: near the phase boundary, critical nuclei of the new phase are comparable in size to the nanocrystal itself. Transformation rates are then unavoidably governed by nanocrystal dimensions. Our results provide a general framework for understanding how nanoconfinement fundamentally impacts broad classes of thermally driven solid-state phase transformations relevant to hydrogen storage, catalysis, batteries and fuel cells.

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Figure 1: Pd nanocube characterization and luminescence.
Figure 2: Nanocube hysteresis loops and size-dependent thermodynamics.
Figure 3: Nanoconfined, thermally driven nucleation provides a natural explanation for the strong size dependence of nanocube kinetics.
Figure 4: Free energy barriers to phase change are controlled, near phase coexistence, by nanocube size.
Figure 5: Nanocube kinetics resulting from sudden, large pressure changes suggest that phase change begins at nanocube surfaces.

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Acknowledgements

We would like to thank R. Hauge at Rice University, Houston, Texas for help with the optical cell. We would also like to acknowledge A. Schwartzberg, T. Mattox, R. Buonsanti, A. Ruminski, T. Kyukendall, I. Tamblyn and L. Maibaum for helpful discussions. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under Contract No. DE-AC02-05CH11231. J.J.U. and R.B. are supported under the US Department of Energy Hydrogen Storage Program, B&R code KC0202020. C.L.P. and A.J. are supported under Mohr Davidow Ventures and Berkeley Sensor and Actuators Center. L.O.H. was supported by the Center for Nanoscale Control of Geologic CO2, a US D.O.E. Energy Frontier Research Center, under Contract No. DE-AC02–05CH11231.

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Author notes

  1. Rizia Bardhan & Cary L. Pint

    Present address: Present addresses: Department of Chemical and Biomolecular Engineering, Vanderbilt University, Nashville, Tennessee 37235, USA (R.B.); Department of Mechanical Engineering, Vanderbilt University, Nashville, Tennessee 37235, USA (C.L.P.),

  2. Rizia Bardhan and Lester O. Hedges: These authors contributed equally to this work

Authors and Affiliations

  1. Materials Sciences Division, Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA

    Rizia Bardhan, Lester O. Hedges, Stephen Whitelam & Jeffrey J. Urban

  2. Department of Electrical Engineering and Computer Sciences, University of California, Berkeley, California 94720, USA

    Cary L. Pint & Ali Javey

  3. Berkeley Sensor and Actuator Center, University of California, Berkeley, California 94720, USA

    Cary L. Pint & Ali Javey

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  1. Rizia Bardhan
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Contributions

J.J.U. and R.B. conceived and designed the experiments. R.B. synthesized and characterized the nanoparticles and performed the experiments. C.L.P. designed and built the optical cell; C.L.P. and R.B. built the high-vacuum gas-flow system. L.O.H. and S.W. conceived the simulation protocol, and L.O.H. carried out the simulations. R.B., L.O.H., S.W. and J.J.U. analysed the data and wrote the manuscript. A.J., S.W. and J.J.U. discussed the results and commented on the manuscript.

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Correspondence to Stephen Whitelam or Jeffrey J. Urban.

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Bardhan, R., Hedges, L., Pint, C. et al. Uncovering the intrinsic size dependence of hydriding phase transformations in nanocrystals. Nature Mater 12, 905–912 (2013). https://doi.org/10.1038/nmat3716

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