FisMat2017 - Submission - View

Abstract's title: Core-Shell Structure of Palladium Hydride Nanoparticles Revealed by Combined X-ray Absorption Spectroscopy and X-ray Diffraction
Submitting author: Carlo Lamberti
Affiliation: “Smart Materials” Center Southern Federal University
Affiliation Address: “Smart Materials” Center Southern Federal University, Zorge street 5, 344090 Rostov-on-Don, Russia. and Department of Chemistry, University of Turin, Via Giuria 7, 10125 Turin, Italy
Country: Russia
Oral presentation/Poster (Author's request): Oral presentation
Other authors and affiliations: Aram L. Bugaev, Alexander A. Guda, Viktor V. Shapovalov Lusegen A. Bugaev, Alexander V. Soldatov, (Southern Federal University, Rostov-on-Don, Russia) Kirill A. Lomachenko, (European Synchrotron Radiation Facility, Grenoble, France) Andrea Lazzarini, (inGAP Centre for Research Based Innovation, Department of Chemistry, University of Oslo, Norway) Jenny G. Vitillo, Elena Groppo, (Department of Chemistry, University of Turin, Italy) Riccardo Pellegrini, (Chimet SpA - Catalyst Division, Viciomaggio Arezzo, Italy) Jeroen A. van Bokhoven (ETH Zurich, and Paul Scherrer Institute, Villigen, Switzerland)

We report an in situ, temperature and H2 pressure-dependent, characterization of (2.6 ± 0.4) nm palladium nanoparticles supported on active carbon during the process of hydride phase formation. For the first time the core-shell structure is highlighted in the single-component particles on the basis of a different atomic structure and electronic configurations in the inner “core” and surface “shell” regions. The atomic structure of these particles is examined by combined X-ray powder diffraction (XRPD), which is sensitive to the crystalline core region of the nanoparticles, and by first shell analysis of extended X-ray absorption fine structure (EXAFS) spectra, which reflects the averaged structure of both the core and the more disordered shell. In whole temperature range (0-85 °C), XRPD the analysis confirms the existence of two well-separated α- and β- hydride phases with the characteristic flat plateau in the phase transition regionof the pressure-lattice parameter isotherms. In contrast, first shell interatomic distances obtained from EXAFS exhibit a smoother behavior in the phase transition region, typical for nanostructured palladium. Such difference is explained by distinct properties of bulk “core” which has crystalline structure and sharp phase transition, and surface “shell” which is amorphous and absorbs hydrogen gradually without forming distinguishable α- and β- phases. Combining EXAFS and XRPD we extract, for the first time, the Pd-Pd first-shell distance in the amorphous shell of the nanoparticle, that is significantly shorter than in the bulk core and relevant in catalysis. The core/shell model is supported by the EXAFS analysis of the higher shells, in the frame of the multiple scattering theory, showing that the evolution of the third shell distance (DeltaR3/R3) is comparable to the evolution of (Deltaa/a) obtained from XRPD since amorphous PdHx shell gives a negligible contribution in this range of distances This operando structural information is relevant for the understanding of structure-sensitive reactions. Additionally, we demonstrate the differences in the evolution of the thermal parameters obtained from EXAFS and XRPD along the hydride phase formation.

[1] A. L. Bugaev et al. Catal. Today, 283 (2017) 119; J. Phys. Chem. C., 121 (2017) doi: 10.1021/acs.jpcc.7b04152.