Structural and Thermodynamic Studies of Hydrogen Absorption/Desorption Processes on PdPt Nanoparticles

Hiroshi Akiba, Hirokazu Kobayashi, Hiroshi Kitagawa, Kazutaka Ikeda, Toshiya Otomo, Tomokazu Yamamoto, Syo Matsumura, Osamu Yamamuro

Research output: Contribution to journalArticle

Abstract

This work is motivated by an interesting phenomenon discovered by Kobayashi et al., whereby a phase-separated nanoparticle of the Pd-core and Pt-shell is mixed into a solid solution alloy nanoparticle by repeating hydrogen absorption/desorption processes at 373 K. To investigate the structural change, including the positions of hydrogen atoms and the thermodynamic aspect, we measured the neutron diffraction and enthalpy of hydrogen absorption for Pd0.8Pt0.2 nanoparticles (diameter: 5.0 ± 1.1 nm). Rietveld and atomic pair distribution function (PDF) analyses revealed that D atoms are located at the interstitial octahedral (O) and tetrahedral (T) sites in the solid solution Pd0.8Pt0.2D0.36 nanoparticles, while D atoms are not located at the interstitial sites but trapped somewhere, probably at the surface and at the core-shell interface, in core-shell Pd0.8Pt0.2D0.50 nanoparticles. These results are consistent with the model in which hydrogen atoms play a role in creating defects around the interface to lower the activation energy of the mixing process. The enthalpies of H2 and D2 absorptions in the solid solution Pd0.8Pt0.2 nanoparticles at 298 K and 0.1 MPa are -(20.7 ± 0.1) kJ(H·mol)-1 and -(20.1 ± 0.2) kJ(D·mol)-1, respectively. Both of these values are larger than the corresponding values in Pd nanoparticles, suggesting that the hydrogen absorption sites are stabilized by adding Pt atoms, even though Pt itself does not absorb hydrogen. This unusual and interesting effect is discussed on the basis of the structural and thermodynamic data obtained in this work.

Original languageEnglish
Pages (from-to)9471-9478
Number of pages8
JournalJournal of Physical Chemistry C
Volume123
Issue number14
DOIs
Publication statusPublished - Apr 11 2019

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

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