IRIDE: Interdisciplinary research infrastructure based on dual electron linacs and lasers
This paper describes the scientific aims and potentials as well as the preliminary technical design of RUDE, an innovative tool for multi-disciplinary investigations in a wide field of scientific, technological and industrial applications. IRIDE will be a high intensity "particles factory", based on a combination of high duty cycle radio-frequency superconducting electron linacs and of high energy lasers. Conceived to provide unique research possibilities for particle physics, for condensed matter physics, chemistry and material science, for structural biology and industrial applications, IRIDE will open completely new research possibilities and advance our knowledge in many branches of sci…
Structural evolution of Pt/ceria-zirconia TWC catalysts during the oxidation of carbon monoxide
The structural evolution of two Pt/ceria–zirconia catalysts, characterized by different amounts of supported Pt, was monitored by in situ X-ray diffraction during the anaerobic oxidation of CO at different temperatures. In a first phase, oxygen coming from the surface layers of the ceria–zirconia mixed oxide is consumed and no structural variation of the support is observed. After this induction time, bulk reduction of Pt/ceria–zirconia takes place as a step-like process, while the CO2 production continues at a nearly constant rate. This behavior is totally different from that of the metal-free support in similar reaction conditions, that show a gradual bulk reduction. In repeated oxidation…
Indium Doping in Barium Cerate: the Relation between Local Symmetry and the Formation and Mobility of Protonic Defects
The solid solution series Ba(In,Ce)O3-ä has been investigated with respect to structure, formation, and mobility of protonic defects. Compared to the limited solubility of Y2O3 in BaCeO3 and BaZrO3, the complete solubility of In2O3 is suggested to reflect a relation between absolute hardness of the dopant and the ease of insertion into the hosting lattices. Extended X-ray absorption fine structure (EXAFS) was used to probe the local environment of In3+ in barium cerate: in the surroundings of the dopant, the orthorhombic structure is strongly modified, resulting in an increase of local symmetry. The InO6 octahedra are very regular, and there is no indication for any defect clustering. This …
Local environment of Barium, Cerium and Yttrium in BaCe1−xYxO3−δ ceramic protonic conductors
Abstract Y-doped barium cerate protonic conductors with composition BaCe 1 − x Y x O 3 − δ ( x = 0.02, 0.1, 0.2, 0.3) have been synthesized by sol–gel route, giving by X-ray diffraction tests a homogeneous crystalline phase. A commercial sample BaCe 0.8 Y 0.2 O 3 − δ produced by combustion spray pyrolysis was also provided for comparison aim. The local structure around the cations was studied by X-ray absorption spectroscopy at the K-edges of Ba, Ce and Y. It is demonstrated that the insertion of yttrium in the site of cerium produces a remarkable local distortion of the dopant first-shell octahedral environment that affects also the next coordination shells by a static disorder increas…
Dopants and defects: local structure and dynamics in barium cerates and zirconates
In this paper we present an overview of state-of-the-art EXAFS measurements and data analysis on Ba, Ce, Zr, Y, In and Gd local environments in Y:BaCeO3, In:BaCeO3, Gd:BaCeO3, Y:BaZrO3, and In:BaZrO3, at different temperatures, hydration degrees and doping levels. This approach allows to reach unprecedented insights on the peculiar role of the dopant, and its interactions with the other lattice defects. In particular, we evidence that each different dopant shows unique behavior, depending mainly on its electronic structure, and that the usual criterion of ionic radius matching is not useful to outline an effective doping strategy of proton-conducting perovskites. As what concerns the struct…
Dopant-Host oxide interactions and proton mobility in Gd:BaCeO3
The local structure of Gd:BaCeO3 at different dopant concentrations (2-20%) was studied by X-ray absorption spectroscopy. The EXAFS analysis shows that the environment of the regular Ba2+ and Ce4+ cations is to a limited extent affected by doping. The local structure of gadolinium shows an expansion of the first coordination shell of oxygens, consistent with the ionic radius of Gd3+, but a contraction of the next neighboring shells of cations. In particular, the Ba2+ second neighbors get closer to the dopant, which can be originated by the effective negative charge sharply localized on the dopant. Comparison between EXAFS data of dry and hydrated compounds confirms this interpretation, show…
A new cell for the study of in situ chemical reactions using X-ray absorption spectroscopy
An in situ cell for reductive and oxidative treatments at different temperatures that allows the possibility of recording data as a function of temperature has been designed and constructed for X-ray absorption experiments at the GILDA beamline BM08 of ESRF. The cell is linked to a mass quadrupole spectrometer providing control of the reaction gases and monitoring of the products. The apparatus allows measurements to be performed both in transmission and fluorescence geometry. The cell was tested by studying the CO oxidation reaction promoted by a Pt/ceria-zirconia-supported catalyst. The CO(2) yield is correlated with the structural results confirming the existence of a strong metal-suppor…
EXAFS and XRD study of Pd–Ag bimetallic catalysts supported on pumice from organometallic precursors
Abstract Silver–palladium bimetallic catalysts were supported on pumice following different procedures, based on mild treatments of organometallic precursors. The experiments for the structural characterization of the synthesized samples, wide angle X-ray diffraction (XRD) and X-ray absorption spectroscopy, were carried out at the beamline GILDA of the European Synchrotron Radiation Facility. The analysis of the data demonstrated that alloying took place with a degree of homogeneity depending on the different preparation routes.
Time-resolved X-ray powder diffraction on a three-way catalyst at the GILDA beamline
Time-resolved X-ray diffraction experiments carried out at the beamline BM08-GILDA of ESRF allowed a study of the structural modifications taking place in a Pt/ceria-zirconia catalyst while the CO oxidation reaction was in progress. The capillary tube in which the sample is stored acts effectively as a chemical microreactor that ensures homogeneity of the sample treatments and minimization of diffusion effects. During the flowing of the reactant CO/He mixture, the investigated catalyst undergoes a fast Ce(IV)-Ce(III) partial reduction that involves the release of one O atom for every two reduced Ce cations. Because Ce(III) has a larger ionic radius than Ce(IV), the structural modification p…
Proton Dynamics in In:BaZrO3: Insights on the Atomic and Electronic Structure from X-ray Absorption Spectroscopy
The local structure of Ba2+, Zr4+, and In3+ in In:BaZrO3 is investigated with EXAFS for samples having 0 to 75% In3+ content. It is found that indium can be inserted in any ratio in the host matrix oxide and that the oxygen coordination shell displays an In-O distance very similar to the Zr-O length. In the Zr-rich compositions, there is a preferred dopant-vacancy association that, however, does not give rise to dopant-proton interaction in the hydrated samples. The tendency of Ba2+ to be attracted toward the dopant site is attributed to the electrostatic interaction with the dopant and to the structural rearrangement around the In3+ site. Third cumulant analysis at high temperatures (up to…
Structural characterization of Pd-Ag and Pd-Cu bimetallic catalysts by means of EXAFS, WAXS and XPS
Bimetallic Pd-Ag and Pd-Cu pumice-supported catalysts have been synthesized following different preparation procedures with the aim of improving the selectivity and reactivity of monometallic Pd/pumice systems. The structural characterization, carried out by X-ray Diffraction, X-ray Absorption and X-ray Photoelectron Spectroscopy, allowed to investigate the importance of the preparation procedures in the alloy formation.
Metal-support interaction and redox behavior of Pt(1 wt %)/Ce0.6Zr0.4O2
The catalyst Pt(1 wt %)/Ce(0.6)Zr(0.4)O(2) is studied by CO-temperature programmed reduction (CO-TPR), isothermal oxygen storage complete capacity (OSCC), X-ray absorption spectroscopy (XAS) at the Pt L(III) edge, and in situ X-ray diffraction (in situ XRD), with the aim of elucidating the role of supported metal in CO oxidation by ceria-based three-way catalysts (TWC). The redox behavior of Pt(1 wt %)/Ce(0.6)Zr(0.4)O(2) is compared to that of bare ceria-zirconia. OSCC of redox-aged Pt/ceria-zirconia is twice that of bare ceria-zirconia, and the maximum of CO consumption occurs at a temperature about 300 K lower than redox-aged ceria-zirconia. XAS analysis allows one to evidence the formati…
Local Environment of Yttrium in Y-Doped Barium Cerate Compounds
The local structure of yttrium in Y-doped BaCeO3 compounds was studied using X-ray absorption spectroscopy (XAS) at the Y K-edge. Data analysis shows that the local environment of Y3+ changes, resulting in a distorted octahedron. The structural distortion found does not depend on the dopant amount at the investigated compositions, but on the level of hydration, as clearly demonstrated by the distortion increase in the BaCe0.9Y0.1O3-ä sample after the treatment in O2/H2O. In situ measurements performed in O2/H2O flux, which show that the distortion is retained at 753 K, are also reported. The observed significative structural changes seem to point out a preferential insertion of the hydroxyl…