Crossing the boundary between face-centred cubic and hexagonal close packed: the structure of nanosized cobalt is unraveled by a model accounting for shape, size distribution and stacking faults, allowing simulation of XRD, XANES and EXAFS

The properties of nanostructured cobalt in the fields of magnetic, catalytic and biomaterials depend critically on Co close packing. This paper reports a structural analysis of nanosized cobalt based on the whole X-ray diffraction (XRD) pattern simulation allowed by the Debye equation. The underlying structural model involves statistical sequences of cobalt layers and produces simulated XRD powder patterns bearing the concurrent signatures of hexagonal and cubic close packing (h.c.p. and f.c.c.). Shape, size distribution and distance distribution between pairs of atoms are also modelled. The simulation algorithm allows straightforward fitting to experimental data and hence the quantitative …

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…

Structural, catalytic and electrical investigation on La1-xSrxCr1-yFeyO3- δ as anodes for IT-SOFCs

Ceria-based electrolytes prepared by solution combustion synthesis: The role of fuel on the materials properties

Ce0.8Sm0.2O2 − xpowders were synthesized by solution combustion synthesis using citric acid, cellulose and sucrose as single, or intimately mixed, fuels. The powders were characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, N2sorption at −196 °C, H2-temperature programmed reduction and thermogravimetric analyses. Textural properties of the powders were shaped by the peculiar employed fuel. The study of reducibility revealed that oxygen vacancies formation is mainly influenced by both parameters, specific surface area and total pore volume. The different tendency toward reduction played a key role in sintering under reducing atmosphe…

Metal-support and preparation influence on the structural and electronic properties of gold catalysts

Abstract Nanostructured gold catalysts supported on CeO2 and SiO2 were prepared by the deposition–precipitation (DP) and the solvated metal atom dispersion (SMAD) techniques. The structural and electronic properties of the catalysts were investigated by X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS). Gold was found as small metal nanoparticles (cluster size ∼2 nm) in the SMAD-prepared samples and in ionic state in the DP catalysts. The catalytic activity of the samples was tested in the reaction of low temperature CO oxidation. Gold nanosized particles in a pure metallic state exhibited a worse catalytic performance, both on ceria and…

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 …

Cation Environment of BaCeO3−Based Protonic Conductors II: New Computational Models

Quantum chemical calculations have been carried out to simulate Y-doped BaCeO(3) derivatives. Hartree-Fock energy functional was used to study octahedral site environments embedded in a Pmcn orthorhombic framework, showing local arrangement characterized by Ce-O-Ce, Ce-O-Y, and Y-O-Y (Z-O-Ξ) configurations and including or not hydrogen close to the moieties encompassing those configurations. The latter are, in fact, representative of - and, in our modeling approach, were treated as - local arrangements that could be found in Y:BaCeO(3)-doped materials. The geometrical optimizations performed on the structural models and a detailed orbital analysis of these systems allowed us to confirm and …

Double implantation in silica glass for metal cluster composite formation: a study by synchrotron radiation techniques

Silica glass containing metal clusters is studied for both basic and applied aspects, related to the physics of cluster formation and to the optical properties of these materials. To obtain such composite structure, Cu+ Ni, Au+ Cu, Au+ Ag, Cu+ Co, and Cu+ Ag sequential implantations in fused silica were realized. The resulting systems, after possible annealing in various atmospheres, were studied by synchrotron radiation-based techniques, namely, extended X-ray absorption fine structure (EXAFS) spectroscopy, grazing incidence X-ray diffraction (GIXRD), and grazing incidence small angle X-ray scattering (GISAXS). The unique potential of these techniques is the capability to investigate dilut…

Structure and the metal-support interaction of the Au/Mn oxide catalysts

Gold catalysts with loading 1 and 10 wt % were-prepared by deposition precipitation method with urea over mesoporous manganese oxide, obtained through a surfactant-assisted procedure by using cetyltrimethylammonium bromide (CTAB), followed by treatment with sulphuric acid. For comparison, Au(10 wt %) was also deposited over commercial CeO2 and SiO2 supports. The materials were characterized by XRD and EXAFS at the Mn K and Au L-III edges and XPS. Moreover, the analyses were performed on the samples treated under 1%CO/He, at 250 degrees C for 90 min. The structural and surface results of the as prepared manganese oxide confirmed the formation of gamma-MnO2 along with some amorphous Mn3O4 upo…

DEBYE FUNCTION ANALYSIS OF SYNCHROTRON XRD DATA: STACKING FAULTS AND MICROSTRAINS IN SPHERICAL PALLADIUM CRYSTALLITES

The X-ray determination of the amounts of the phases in samples of isotactic poly(propylene) quenched from the melt at different cooling rates

A new procedure for the determination of the amounts of phases in samples of isotactic poly(propylene) quenched at different cooling rates from the same melted polymer is described. According to the procedure, all the patterns corresponding to the same quenching series are simultaneously analyzed for the amounts of phases so that reliable phase fractions relative to the different samples of the series are achieved. The analysis of the results points out that for increasing cooling rates above 30°C/s a remarkable increase of the mesomorphic phase settles, mainly at the expense of the α-monoclinic one.

X-ray Spectroscopy of (Ba,Sr,La)(Fe,Zn,Y)O3-δIdentifies Structural and Electronic Features Favoring Proton Uptake

Mixed protonic–electronic conducting oxides are key functional materials for protonic ceramic fuel cells. Here, (Ba,Sr,La)(Fe,Zn,Y)O3−δ perovskites are comprehensively investigated by X-ray spectroscopy (in oxidized and reduced states). Extended X-ray absorption fine structure shows that Zn,Y doping strongly increases the tendency for Fe–O–Fe buckling. X-ray absorption near-edge spectroscopy at the Fe K-edge and X-ray Raman scattering at the O K edge demonstrate that both iron and oxygen states are involved when the samples are oxidized, and for the Zn,Y doped materials, the hole transfer from iron to oxygen is less pronounced. This can be correlated with the observation that these material…

Phase analysis and oxygen strorage capacity of ceria-lanthana-based TWC promoters prepared by sol-gel routes

Ceria–lanthana-based promoters of three-way catalysts are synthesized by two different sol–gel routes, involving nitrate precursors. The oxygen uptake ability of these compounds is measured by O2 chemisorption. The specific surface area is determined by N2 adsorption (BET). X-ray diffraction data are analyzed by Rietveld refinement, demonstrating that lanthanum forms solid solution with CeO2; its total amount in ceria depends on the competitive formation of La–Al mixed oxides and on the synthetic method. The O2 uptake ability is essentially determined by the La content in the ceria–lanthana solid solution, while it is independent on the surface area and on the CeO2 particle size. The O2 upt…

Electrode–Electrolyte Compatibility in Solid-Oxide Fuel Cells: Investigation of the LSM–LNC Interface with X-ray Microspectroscopy

Ca:LaNbO4 (LNC) constitutes the last real breakthrough in high-temperature proton conductors, with better chemical and mechanical stability with respect to cerate and zirconate perovskites. However, the low amount of bivalent dopant that can be hosted in the LaNbO4 matrix poses a limit to the proton concentration in the electrolyte. Using synchrotron X-ray microspectroscopy, we investigated the compatibility of annealed LNC/LSM electrolyte/cathode bilayers for proton-conducting SOFCs. The element maps are complemented by microEXAFS and microXANES, giving information on the fate of different cations after diffusion. The X-ray microspectroscopy approach described here is applied for the first…

Nanostructured gold catalysts for low temperature CO oxidation

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…

Some structurally disordered models for poly(tetrafluoroethylene) were elaborated and the corresponding calculated X-ray diffraction patterns compared with experimental patterns. This and differential scanning calorimetry results suggest some differences between the virgin powder and a sintered polycrystalline plate of poly(tetrafluoroethylene). These differences may be related to the crystal phase transitions that occur in a range of temperatures close to room temperature.

Indium doping of proton-conducting solid oxides

Solid oxides protonic conductors are prepared by doping the pure matrix compounds with cationic species. Barium cerate and barium zirconate are perovskite-like compounds, characterized by a network of corner-sharing MeO6 octahedra (Me=Ce, Zr). Barium lies in the cavities between octahedra. Insertion of trivalent species in the octahedral site involves the formation of charge- compensating oxygen vacancies, that can be filled by hydroxyls coming from dissociative water absorption. Then, proton delocalization among structural oxygens ensures conductivity. The most effective conductors are obtained by yttrium doping that, on the other hand, enters only in limited amounts in both BaZrO3 and BaC…

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…

Structure of the Metal–Support Interface and Oxidation State of Gold Nanoparticles Supported on Ceria

An Au/CeO2 model catalyst was prepared by deposition–precipitation, with the aim of obtaining a sample suitable for a detailed X-ray absorption fine structure (XAFS) analysis of the gold–ceria interface structure. The results demonstrate the existence of a large interface between the gold particle and the support oxide, characterized by well-defined Au–O and Au–Ce interactions extending up to ∼6.4 A. The complex interface structure is retained after CO treatment up to 250 °C and subsequent reoxidation at 400 °C. The analysis of the XANES spectra, and the Au–O distance of 2.21 A, longer than Au–O bond lengths previously reported for Au/ceria catalysts, suggest a low oxidation state for the g…

Ionic conductivity of nanocrystalline heavily acceptor doped ceria: The role of the local atomic order

Acceptor doped ceria (CeO2) is a material that over the years has attracted much interest for applications in solid oxide fuel cells and oxygen membranes. This study aims at systematically investigating how the local atomic order and the dopant distribution affect the ionic transport of nanocrystalline CeO2 ceramics doped with samarium, erbium and ytterbium, with concentrations ranging between 10 and 30 at.%. For this purpose, a.c. electrochemical impedance spectroscopy together with Raman and fluorescence spectroscopy as well as XRD and EXAFS analysis have been carried out. In order to have detailed information on the bulk properties of these compositions also microcrystalline samples have…

Solid-state compatibility of Ca:LaNbO4 with perovskite cathodes: Evidences from X-ray microspectroscopy

The solid-state compatibility between calcium-doped lanthanum niobate and three perovskite cathode materials was investigated using two X-ray microbeam techniques, micro X-ray fluorescence and micro X-ray absorption spectroscopy. The cathode powders (lanthanum strontium ferrite, either cobalt or copper-doped, and lanthanum strontium cobaltite) in contact with the dense electrolyte pellet were annealed at 1150 degrees C for 12-144 h to simulate the effect of thermal stresses due to fabrication and long-term operation. As a result, several interdiffusion phenomena were then observed on the bilayer cross-sections: in particular, the chemical state and coordination environment of calcium, iron,…

Covalent and Ionic Functionalization of HLN Layered Perovskite by Sonochemical Methods

We describe the functionalization of the layered perovskite HLaNb2O7 with n-propanol, n-decanol, 3-mercaptopropyl-trimethoxysilane, imidazole, n-decylamine, and histamine. The use of sonication is found to significantly improve the reaction yield and to reduce the reaction time, compared to conventional thermal treatment under reflux. The obtained intercalates are thoroughly characterized through the use of several complementary experimental techniques (scanning electron microscopy, IR spectroscopy, X-ray diffraction, thermogravimetric analysis, magic-angle spinning NMR), clarifying their structure and chemical bonding. The implications for the design of inorganic–organic composite material…

Structure and oxide ion conductivity: local order, defect interactions and grain boundary effects in acceptor-doped ceria

The long-range and short-range structure of nanocrystalline and microcrystalline acceptor-doped ceria is investigated by a combined approach using EXAFS, XANES, Raman, and XRD, and correlated with the oxide-ion conductivity in the bulk and in grain boundaries. Compared to Yb3+ and Er3+, the positive influence of Sm3+ is attributed to the ability to repel oxygen vacancies, and to keep a localized disorder around the dopant. The long-range structural analysis shows lattice contraction for Yb- and Er-doping and lattice expansion for Sm-doping. The short-range analysis around the dopants and cerium highlights that a more complex structural rearrangement has to be assumed to explain the compleme…

Liquid phase selective oxidation of benzyl alcohol over Pd–Ag catalysts supported on pumice

Abstract Selective oxidation of benzyl alcohol to benzaldehyde was carried out over pumice supported bimetallic and monometallic Pd and Ag catalysts. Preliminary kinetic studies were performed at 333 K in autoclave, at pressure of 2 atm in pure oxygen. Under these conditions, small amounts of benzoic acid were detected with the monometallic Pd pumice being the most active catalyst. The reaction was also carried out under flowing oxygen at atmospheric pressure and at 348 K. Under these conditions, the selectivity to benzaldehyde was 100%. The catalytic activity of the catalysts was measured after different oxidation and reduction treatments at high temperature. In addition, two mechanical mi…

Dopant Clusterization and Oxygen Coordination in Ta-Doped Bismuth Oxide: A Structural and Computational Insight into the Mechanism of Anion Conduction

Bi2O3 in its fluorite-like form can be obtained either at 730-824 °C, showing the highest oxide-ion conduction known so far, or by doping. We present a comprehensive appraisal of the local atomic structure of Ta-doped Bi2O3 investigating by X-ray absorption spectroscopy the aggregation motifs of Ta5+ and the interaction between dopants and oxygen vacancies. Using periodic density functional theory simulations, we show that the connection of Ta4O18 aggregates is energetically favorable. We find that the local coordination of Bi3+ and its electronic structure, as seen from the calculated density of states (DOS), are invariably determined by the Bi 6s2 lone pair in both doped and undoped Bi2O3…

Relationship between thymidylate synthase expression and p53 levels with the treatment of cyclophsphamide, methotrexate, 5-fluorouracil chemotherapy ( CMF)versus docetaxel ( TXT) in locally advanced carcinoma of the breast

10546 Background: Adjuvant chemotherapy is used in the treatment of breast carcinoma independently of axillar node involvement. Different drug combinations such as CMF, FAC, FEC are still used; recently new drugs such as TXT (NEJM 332:1004,1997) show activity and are used also in adjuvant chemotherapy. 5 Fluorouracil (5Fu), a drug involved in main therapeutic regimens, blocks Thymidylate Synthase (TS), an enzyme involved in the DNA synthesis. TS not only links its own mRNA, but also p53 mRNA, inhibiting post transcriptional p53 protein synthesis. TS protein overexpression (Cancer Res 55:1407,1995), and/or its absence (Cancer Res 61:1421,2001) are some of the main mechanisms of 5-Fu drug re…

Interface Solid-State Reactions in La0.8Sr0.2MnO3/Ce0.8Sm0.2O2 and La0.8Sr0.2MnO3/BaCe0.9Y0.1O3 Disclosed by X-ray Microspectroscopy

The stability of the electrode/electrolyte interface is a critical issue in solid-oxide cells working at high temperatures, affecting their durability. In this paper, we investigate the solid-state chemical mechanisms that occur at the interface between two electrolytes (Ce0.8Sm0.2O2, SDC, and BaCe0.9Y0.1O3, BCY) and a cathode material (La0.8Sr0.2MnO3, LSM) after prolonged thermal treatments. Following our previous work on the subject, we used X-ray microspectroscopy, a technique that probes the interface with submicrometric resolution combining microanalytical information with the chemical and structural information coming from space-resolved X-ray absorption spectroscopy. In LSM/BCY, the …

Model Pumices Supported Metal Catalysts

The catalyzed, selective hydrogenation, in liquid phase, of 1,3-cyclooctadiene was studied on a series of Pd catalysts supported on natural pumice, model pumices (with variable content of alkali metal ions), silica, and sodium-doped silica. At constant pressure of H2(1 atm.) the reaction follows a zero-order kinetic for all the Pd catalysts. At low metal dispersion (Dx < 20%), Pd/pumice catalysts exhibit higher activity as compared to Pd/silica catalysts; the turnover frequency is maintained even at high metal dispersion in Pd/pumice but Pd/silica and Pd/model pumices without alkali ions show a decrease in activity. At increasingDx, the binding energy shift of Pd 3dlevel is negative in Pd/p…

Long-Range and Short-Range Structure of Proton-Conducting Y:BaZrO3

Yttrium-doped barium zirconate (BZY) is the most promising candidate for proton-conducting ceramics and has been extensively studied in recent years. The detailed features of the crystal structure, both short-range and long-range, as well as the crystal chemistry driving the doping process, are largely unknown. We use very high resolution X-ray diffraction (HR-XRD) to resolve the crystal structure, which is very slightly tetragonally distorted in BZY, while the local environment around Zr4+ and Y3+ is probed with extended X-ray absorption fine structure (EXAFS), and the symmetry and vibrations are investigated by using Raman spectroscopy. It is found that barium zirconate shows some degree …

Highly Stable Thin Films Based on Novel Hybrid 1D (PRSH)PbX3 Pseudo-Perovskites

In this study, the structure and morphology, as well as time, ultraviolet radiation, and humidity stability of thin films based on newly developed 1D (PRSH)PbX3 (X = Br, I) pseudo-perovskite materials, containing 1D chains of face-sharing haloplumbate octahedra, are investigated. All films are strongly crystalline already at room temperature, and annealing does not promote further crystallization or film reorganization. The film microstructure is found to be strongly influenced by the anion type and, to a lesser extent, by the DMF/DMSO solvent volume ratio used during film deposition by spin-coating. Comparison of specular X-ray diffraction and complementary grazing incidence X-ray diffract…

Cation Environment in BaCeO3-Based Protonic Conductors: a Computational Study

Geometry calculations were performed on pure BaCeO(3) fragments and on Y- and In-doped derivatives. HF and DFT approaches were used to investigate monoclinic and orthorhombic structures. The computational methods, structural models, and electronic structure investigation protocols were tuned taking into consideration and balancing the consistency of the results against the computational cost. The calculated structures and energetics parameter, as well as the detailed orbital analysis performed on the corresponding BaCeO(3) derivatives allowed us to explain experimental findings and to develop a procedure to study the cationic octahedral environment of doped X:BaCeO(3) (X = Y, In) and undope…

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…

EXAFS study of ceria–lanthana-based TWC promoters prepared by sol–gel routes

Extended X-ray absorption fine structure (EXAFS) experiments at the Ce K- and La K-edges were performed on ceria–lanthana–alumina three-way catalysts promoters prepared by sol–gel routes, in order to investigate the effect of lanthanum doping on the ceria structure. The formation of Ce1−xLaxO2−x/2 solid solution, already observed by X-ray diffraction, was confirmed by EXAFS analysis, while no experimental evidence of a Ce–Al interaction was found. In presence of cerium and aluminum, lanthanum is involved in the formation of solid solution with CeO2 and of La–Al compounds. When the La:Al molar ratio is sufficiently high, the growth of a tridimensionally ordered LaAlO3 perovskite compound is …

Proton sponge lead halides containing 1D polyoctahedral chains

Hybrid one-dimensional lead halides, containing the protonated 1,8-bis(dimethylamino)naphthalene moiety (C14H19N2, monoprotonated "proton sponge"), were prepared by simple one-pot methods and investigated in terms of crystal structure, morphology, thermal stability and electronic properties. The as-precipitated (C14H19N2)PbBr3 and (C14H19N2)PbI3 species are isostructural and crystallize in the orthorhombic Pbca space group, resulting in 1D crystal phases with ([PbX3](-))(infinity) chains (built by face-sharing [PbX6] octahedra; X = Br, I), among which the (C14H19N2)(+) cations are inserted. The two compounds display complete miscibility in the solid state: both (C14H19N2)PbI2Br and (C14H19N…

Toward tailorable surfaces: a combined theoretical and experimental study of lanthanum niobate layered perovskites.

A comprehensive theoretical investigation of the MLaNb2O7 (M = H, Li, Na, K, Rb, and Cs) series of ion-exchangeable layered perovskite is presented. These perovskites are in particular interesting in view of their potential applications as inorganic supports for the design of new hybrid inorganic-organic proton conductors. In particular, their structural and electronic properties have been investigated by periodic calculations in the framework of Density Functional Theory, using different exchange-correlation functionals. A general very good agreement with the available experimental (XRD, NPD, and EXAFS) data has been found. The structure of the protonated HLaNb2O7 form has also been furthe…

Bi3+doping in 1D ((CH3)3SO)PbI3: A model for defect interactions in halide perovskites

The recently described monodimensional hybrid pseudo-perovskite ((CH3)3SO)PbI3 exhibits complete Pb2+/Bi3+ miscibility in the B site. Heterovalent substitution imposes that charge-compensating defects are introduced in the lattice as well. This paper reports the energetics of point defects and the interaction between charge-compensating defects that occur upon Bi3+ doping in ((CH3)3SO)PbI3. Periodic DFT simulations were employed to analyze the formation energy of Pb2+ vacancies, (CH3)3SO+ vacancies, iodide vacancies, or the insertion of interstitial iodide ions. Solid solutions with a large Bi3+ content were modeled considering different charge compensation defects (Pb2+ vacancies, (CH3)3SO…

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.

Heterovalent BiIII/PbII ionic substitution in one-dimensional trimethylsulfoxonium halide pseudo-perovskites (X = I, Br)

We report on the synthesis and characterization of novel lead and bismuth hybrid (organic-inorganic) iodide and bromide pseudo-perovskites (ABX3) containing the trimethylsulfoxonium cation (CH3)3SO+ (TMSO) in the A site, Pb/Bi in the B site, and Br or I as X anions. All of these compounds are isomorphic and crystallize in the orthorhombic Pnma space group. Lead-based pseudo-perovskites consist of one-dimensional (1D) chains of face-sharing [PbX6] octahedra, while in the bismuth-based ones, the chains of [BiX6] are interrupted, with one vacancy every third site, leading to a zero-dimensional (0D) local structure based on separated [Bi2I9]3- dimers. Five solid solutions for the iodide with di…

Activated Biochar From Posidonia Oceanica. A New Adsorbent Material of Hydrocarbons from Wastewater

Environmental pollution by petroleum derivatives is a very current topic. In particular, low concentration of this kind of pollutants can seriously compromise the life of animals and plants of aquatic ecosystems (Yu, 2017). The current legislation provides that bilgewater, wastewater produced by boats, can be discharged directly into the sea only if the total hydrocarbon concentration not exceds 15 mg L-1. In this work, new activated carbons were tested as adsorbent materials of oil / hydrocarbons from wastewater. Moreover, an instrumental technique able to quickly measure the required low hydrocarbons concentration is also proposed. The new activated carbons were obtained from bio-oil prod…

Structural and electrochemical investigation on re-cast Nafion membranes for polymer electrolyte fuel cells (PEFCs) application

Abstract Starting from a 5 wt% ion power Nafion® solution and dissolving the dry residue in a suitable solvent (10 wt% solution in dimethylacetammide), re-cast Nafion films were developed for polymer electrolyte fuel cells (PEFCs) application. The used Doctor-Blade casting technique allowed to prepare scaled-up membranes comparable to the commercial Nafion ones with good mechanical resistance, thickness homogeneity and an excellent reproducibility. The differences between the re-cast membrane nanostructure and that of the commercial Nafion were investigated by synchrotron small-angle X-ray scattering. The obtained re-cast membrane shows at ambient conditions a semi-crystalline structure wit…

Local environment of yttrium in yttrium-doped barium cerate

Local structure of gallate proton conductors

Lanthanum barium gallate proton conductors are based on disconnected GaO4 groups. The insertion of hydroxyls in the LaBaGaO4 network proceeds through self-doping with Ba2+, consequent O2- vacancy formation to fulfill charge neutrality. With a structural investigation on self-doped LaBaGaO4 oxides using synchrotron XRD and EXAFS on the Ga K-edge, we find that: (a) the GaO4 tetrahedra retain their size throughout the whole series; (b) the GaO4 tetrahedra rotate as rigid bodies on hydration, leading to the formation of a network of shorter O-O configurations that are stabilized by hydrogen bonds; (c) contraction of the lattice occurs along the a unit cell axis, as a consequence of an overall s…

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…

Structure of natural water-containing glasses from Lipari (Italy) and Eastern Rhodopes (Bulgaria): SAXS, WAXS and IR studies

Abstract Two natural water-containing glasses with rhyolite composition originating from two different areas (perlite from Lipari, Italy, and expanded perlite from the Eastern Rhodopes, Bulgaria) have been characterised for chemical composition, atomic structure and specific surface area, with the ultimate goal of exploitation of volcanic glasses as carriers for heterogeneous metal catalysts. The two samples have similar chemical composition and total water content. The local structure, as determined by radial distribution function analysis of the wide angle X-ray scattering patterns, is similar, the medium-range structure being slightly more ordered for the Lipari glass. These results are …

HYDROCARBONS REMOVAL FROM BILGE WATER BY ADSORPTION ONTO ACTIVATED BIOCHAR FROM POSIDONIA OCEANICA

The normal operations carried out on the boats during navigation generate waste waters such as oily bilge water. The latter is the aqueous mixture of potential pollutants of different origins and types: oily fluids, lubricants and greases, cleaning fluids and other wastes that accumulate in the lower part of the vessel [1,2]. The current legislation provides that they can be discharge directly into the sea if the concentrations of some components are below the expected limits. In particular, with regard to oil / hydrocarbons contamination, the current regulatory limit is 15 mg L-1 of total hydrocarbons. The present work starts from a public/private partnership funded by a grant of the Minis…

Modeling bismuth insertion in 1D hybrid lead halide TMSO(Pb x Bi y )I3 pseudo-perovskites

Abstract The structures of the disordered 1D (pseudo-)perovskites of general TMSO(Pb x Bi y )I3 formulation [TMSO = (CH3)3SO+], obtained by doping the TMSOPbI3 species with Bi3+ ions, are investigated through the formulation of a statistical model of correlated disorder, which addresses the sequences of differently occupied BI6 face-sharing octahedra (B = Pb, Bi or vacant site) within ideally infinite [(BI3)−] n chains. The x-ray diffraction patterns simulated on the basis of the model are matched to the experimental traces, which show many broad peaks with awkward (nearly trapezoidal) shapes, under the assumption that the charge balance is fully accomplished within each chain. The analysis…

X-ray Absorption under Operating Conditions for Solid-Oxide Fuel Cells Electrocatalysts: The Case of LSCF/YSZ

We describe a novel electrochemical cell for X-ray absorption spectroscopy (XAS) experiments during electrical polarization suitable for high-temperature materials such as those used in solid oxide fuel cells. A half-cell LSCF/YSZ was then investigated under cathodic and anodic conditions (850 &deg

A real-space approach to the analysis of stacking faults in close-packed metals: G(r) modelling and Q-space feedback

An R-space approach to the simulation and fitting of a structural model to the experimental pair distribution function is described, to investigate the structural disorder (distance distribution and stacking faults) in close-packed metals. This is carried out by transferring the Debye function analysis into R space and simulating the low-angle and high-angle truncation for the evaluation of the relevant Fourier transform. The strengths and weaknesses of the R-space approach with respect to the usual Q-space approach are discussed.

Dynamic Role of Gold d-Orbitals during CO Oxidation under Aerobic Conditions

High-energy-resolution fluorescence detection-X-ray absorption near-edge structure (HERFD-XANES) at the Au L3 edge was used to study gold catalysts supported on ceria in order to unravel the role of gold 5d orbital modifications during the activation of molecular oxygen. The variations in the HERFD-XANES resonance peak, which are directly correlated with the d-band occupancy, were monitored in situ during the redox process of the CO oxidation at room temperature under both aerobic and anaerobic conditions. Interestingly, upon the oxidation treatment and also during the aerobic CO oxidation treatment, the gold d-band fluctuates around an average value, proving that the gold clusters are part…

XPS study of supported gold catalysts:the role of Au0 and Au+? species as active sites.

Gold nanoparticles supported on different oxides (SiO2, CeO2 and TiO2) were prepared by the SMAD (solvated metal atom dispersion) and deposition–precipitation (DP) techniques. The physical and chemical characterization of the catalysts was performed by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) and the catalytic activity was tested during the reaction of low temperature CO oxidation. The structural and surface analyses evidenced the presence of small gold crystallites (cluster size ∼2–5 nm) in all the SMAD-prepared samples and oxidized gold species in the case of the DP catalysts. A different surface distribution of ionic gold species was found on the different suppo…

Long-Term Stability of TiS2–Alkylamine Hybrid Materials

Layered TiS2 intercalated with linear alkylamines has recently attracted significant interest as a model compound for flexible n-type thermoelectric applications, showing remarkably high power factors at room temperature. The thermal and, particularly, environmental stability of such materials is, however, a still an open challenge. In this paper, we show that amine-intercalated TiS2 prepared by a simple mechanochemical process is prone to chemical decomposition through sulfur exsolution, and that the presence of molecular oxygen is likely to mediate the decomposition reaction. Through computational analysis of the possible reaction pathways, we propose that Ti-N adducts are formed as a con…

CO Oxidation on Cationic Gold Clusters: A Theoretical Study

Aiming at understanding the elementary steps governing the oxidation of CO catalyzed by dispersed or supported gold nanoclusters, the reactivity of molecular species, such as O2 and CO, on neutral and positively charged Au13 clusters have been studied using a DFT approach. Two CO oxidation mechanisms have been simulated, involving respectively the adsorption of CO and O2 on adjacent catalytic sites (two-sites mechanism) and the competitive interaction of the reactants on the same site (single-site mechanism). It is demonstrated that in the former scheme a definite interaction of CO and O2 with both the charged and neutral cluster is effective, but that a chemical reaction between the adsorb…

Study of the long-period changes in samples of isotactic poly(propylene) obtained by quenching from the melt and subsequent annealing at different temperatures

The structural modifications induced in samples of isotactic poly(propylene) obtained by quenching from the melt at 100°C/s and subsequently annealed at 40, 60 and 80°C for different annealing times have been studied using simultaneous wide-angle and small-angle X-ray scattering at the synchrotron radiation source of DESY. The occurrance of two different long-period values is demonstrated. These values are related to the mesomorphic phase, existing in the starting quenched material, and to the α-monoclinic one, which settles during the annealing process, respectively.

Effects of capping agent on cobalt nanoparticles

The achievement of high information density and fast recording rate in memory devices crucially depends on the structure of magnetic domains. In this paper cobalt nanoparticles are synthesised using two capping agents (TOA, ODA) and two different preparation routes: thermal decomposition (TD) and Solvated Metal Atom Dispersion (SMAD). The interaction of capping agents with free metal clusters and their influence on Co nanoparticles size, atomic structure and oxidation state is investigated by means of X-ray diffraction and X-ray absorption spectroscopy.

The Effect of Ni Doping on the Performance and Electronic Structure of LSCF Cathodes Used for IT-SOFCs

We investigated the effect of nickel doping on the electronic structure and performance of nanostructured La0.6Sr0.4Co0.2Fe0.8-0.03Ni0.03O3-delta prepared by the one-pot sol gel method. The commercial undoped La0.6Sr0.4Co0.2Fe0.8O3-delta (ISCF0.8) was used as reference. Moreover, for comparison, Ni (3 mol %) was deposited by wetness impregnation over the La0.6Sr0.4Co0.2Fe0.8O3-delta. We show by in situ X-ray absorption spectroscopy at 900 degrees C under air flow that nickel enters the B perovskite site of the material and favors the stabilization of the cobalt oxidation state, as evidenced by the delay in the decrease of the average Co valence with respect to undoped samples. Our results a…

Matrix metalloproteinase-1 is differentially expressed in signet ring cell, and intestinal colorectal carcinomas histotypes

14564 Background: Signet ring cell colorectal carcinoma ( SRCC) pure is an infrequent and highly malignant variant of colorectal cancer, while this histological component is present in 30% of all colorectal carcinomas. In our previous studies we compared the E- Cadherin, β- Catenin, Fibronectin, Ki 67 and Thymidylate Synthase (TS) expression of SRCC, the intestinal type of colorectal carcinoma (ICRC) to try to explain the pathogenesis, the aggressiveness and the low 5 Fluorouracil (5FU) responsiveness of these tumours. We found that all SRCCs had very low levels of all markers and were in the post- mitotic phase of the cell cycle. To understand their high metastatic capability we assessed …

Dopants and defects in proton-conducting perovskites

Many doped perovskites show high proton conductivity at intermediate to high temperatures (500- 900 °C), which has opened possibilities for many prospected applications in energy conversion (fuel cells), and electrochemical devices. In a doped perovskite, e.g. BaCe1-xYxO3-y, oxygen vacancies are created by charge compensation, and can eventually react with air moisture to form structural protonic defects. The sluggish nature of the proton, which is practically invisible to most structural analyses, and poses enormous problems to quantum chemistry, has surely contributed to slow down the progress in the understanding of these materials: in fact, the conduction dynamics and its interplay with…

Distorted f.c.c. arrangement of gold nanoclusters: a model of spherical particles with microstrains and stacking faults

The structures of two samples of gold nanoclusters supported on silica were studied by X-ray powder diffraction (XRD) and X-ray absorption spectroscopy. The data relative to both techniques were analysed by an approach involving simulation based on structural models and fitting. The XRD model concerned a distorted f.c.c. (face-centred cubic) arrangement, with microstrains and parallel stacking faults in approximately spherical particles; as an alternative possibility, a linear combination of ordered f.c.c. and noncrystalline (decahedral and icosahedral) particles was also taken into account. Both approaches gave calculated patterns closely resembling the experimental data. X-ray absorption …

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…

Alumina supported Pt(1%)/Ce0.6Zr0.4O2 monolith: Remarkable stabilization of ceria–zirconia solution towards CeAlO3 formation operated by Pt under redox conditions

Abstract A structured Pt(1 wt%)/ceria–zirconia/alumina catalyst and the metal-free ceria–zirconia/alumina were prepared, by dip-coating, over a cordierite monolithic support. XRD analyses and Rietveld refinements of the structural data demonstrate that in the Pt supported catalysts ceria–zirconia is present as a Ce 0.6 Zr 0.4 O 2 homogeneous solid solution and that the deposition over the cordierite doesn’t produce any structural modification. Moreover no Pt sintering occurs. By comparing the XRD patterns recorded on Pt/ceria–zirconia/alumina and ceria–zirconia/alumina after three redox cycles, it results that Pt, favouring the structural reorganization of the ceria–zirconia into one cubic …

STACKING-FAULTS IN VERY FINE PALLADIUM PARTICLES SUPPORTED ON PUMICE

By means of an X-ray diffraction study, carried out with best-fitting procedures, of the asymmetry and peak maximum shifts of some reflections, stacking-faults in the FCC lattice of very fine palladium particles supported on pumice were detected using the Warren-Wagner-Cohen theoretical approach.

Dopant-matrix interaction in solid oxide electrolytes and electrodes

Materials for solid oxide fuel cells (SOFC) are extensively investigated aiming at achieving better performances and device durability in view of the hopefully next implementation of hydrogen technology for the production of energy. This contribution deals with the structural aspects of the interaction of dopants with the solid matrix, either for electrodes or electrolytes. The report concerns materials that are likely fit for implementation, such as ceria-based electrolytes and mixed-oxide electrodes. However, in view of the importance of achieving a deeper insight in the mechanism of solid-state O2- conduction, results about Bi2O3 compounds are also reported. Finally, the host matrix-dopa…

Structural and morphological properties of Co-La catalysts supported on alumina/lanthana for hydrocarbons oxidation

Abstract Two Al 2 O 3 (24 wt%)–La 2 O 3 (76 wt%) supported Co–La oxides with Co loading 4 wt% and different La content (1 and 9 wt%) were prepared by co-impregnation of the support, the aluminum–lanthanum oxide, with cobalt and lanthanum nitrates in aqueous solution and successive calcination at 800 °C for 4 h. The alumina–lanthana was synthesized by the sol–gel method. The samples were characterized by X-ray diffraction (XRD) and Rietveld refinement in order to identify the crystalline phases and their relative weight. H 2 -TPR (Temperature Programmed Reduction) experiments were recorded with the aim to identify the different Co phases present. Co 3 O 4 and LaCoO 3 were formed for La loadi…

Synthesis and Characterization of a cordierite monolith supported Pt(1%)/Ce0.6Zr0.4O2 catalyst for TWC applications

Structure and dynamics of water confined in silica hydrogels: X-ray scattering and dielectric spectroscopy studies.

We have used a sol-gel technique to obtain optically transparent hydrogels in which water is confined within a 3D silica matrix. In this work we report X-ray scattering and dielectric spectroscopy measurements on samples having different aging times and compare them with previously obtained results with near-infrared (NIR) absorption spectroscopy. X-ray scattering at room temperature enables to characterize the structure and size of the matrix pores and the non-uniform distribution of water inside the hydrogel. Broad band dielectric spectroscopy in the temperature range 130-280 K enables to study water dynamics. In aged hydrogels two relaxations are clearly evident and show characteristic t…

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.

Effects of Grain Boundary Decoration on the Electrical Conduction of Nanocrystalline CeO2

In this study, we investigate the effect of decorating the grain boundaries of nanocrystalline undoped ceria on the electrical transport properties. For the decoration, different acceptors (Yb, Y, Bi) were chosen. On decoration, the conduction switches from electronic to ionic. Upon sintering the grains are characterized by a core-shell configuration, in which the core remains undoped while the shell is heavily doped as a consequence of the diffusion of the acceptors toward the grain interior. The shell dominates the overall transport properties of the nanocrystalline ceria and is found to be in the mesoscopic regime.

Direct Methane Oxidation on La1-xSrxCr1-yFeyO3-δ perovskite-type oxides as Potential Anode for Intermediate Temperature Solid Oxide Fuel Cells

Abstract La1−xSrxCr1−yFeyO3−δ (x = 0, 0.1, 0.15, 0.2; y = 0, 0.3, 0.5) perovskite-type oxide powders were synthesized by solution combustion synthesis and characterized by X-ray diffraction, X-ray photoelectron spectroscopy and H2-temperature programmed reduction. Selected compositions were studied by CH4-temperature programmed reduction in the absence and in the presence of H2S. Temperature programmed oxidation and structural characterizations were performed in order to discriminate the nature of residual deposits on the catalyst surface. The study about reduction in different methane-based mixture revealed that total and partial methane oxidation occurred in the range ∼450–1000 °C indepen…

FROM INTERCONNECTORS TO ANODE MATERIALS FOR IT-SOFCs:THE ROLE OF IRON IN La1-xSrxCr1-yFeyO3-δ

Effect of Alkali Ions on the Amorphous to Crystalline Phase Transition of Silica

Abstract The effect of the addition of alkali ions to commercial amorphous silica, generally used as support for heterogeneous catalysts, has been investigated from the point of view of morphological and structural changes. Samples of alkali-doped silica were prepared by impregnation and subsequent calcination at various temperatures. The structural effect of Li, Na, K, and Cs was determined by use of techniques such as wide-angle (WAXS) and small-angle X-ray scattering (SAXS). The WAXS diffractograms, analyzed with the Rietveld method using the GSAS program, allowed qualitative and quantitative identification of the fraction of the different silica polymorphs like quartz, tridymite, and cr…

Effect of the capping agents on cobalt nanoparticles

The achievement of high information density and fast recording rate in memory devices crucially depends on the structure of magnetic domains. In this paper cobalt nanoparticles are synthesised using two capping agents (TOA, ODA) and two different preparation routes: thermal decomposition (TD) and Solvated Metal Atom Dispersion (SMAD). The interaction of capping agents with free metal clusters and their influence on Co nanoparticles size, atomic structure and oxidation state is investigated by means of X-ray diffraction and X-ray absorption spectroscopy.

Crystal Structure and Local Dynamics in Tetrahedral Proton-Conducting La1-xBa1+xGaO4

La1-xBa1+xGaO4-0 (LBG) compounds, based on unconnected GaO4 moieties, were recently proposed as proton conductors. Protonic defects in the lattice are inserted through self-doping with Ba2+, to create oxygen vacancies subsequently filled by hydroxyl ions. We present a combined structural analysis on self-doped LBG using X-ray diffraction (XRD) and X-ray absorption (EXAFS): these results unravel the finer structural details on the short-range and long-range scales, and they are correlated with the dynamical properties of protonic conduction coming from vibrational spectroscopy. The structure of the GaO4 groups is independent of the oxide composition. On hydration, an array of short intertetr…

Theoretical insights into inorganic-organic intercalation products of the layered perovskite HLaNb2O7: perspectives for hybrid proton conductors

The modification of metal oxide surfaces with organic moieties has been widely studied as a method of preparing organic-inorganic hybrid materials for various applications. Among the inorganic oxides, ion-exchangeable layered perovskites are particularly interesting, because of their appealing electronic and reactive properties. In particular, their protonated interlayer surface can be easily functionalized with organic groups allowing the production of stable hybrid materials. As a further step in the design of new inorganic-organic hybrid proton conductors, a combined experimental and theoretical study of two intercalated compounds (propanol and imidazole) in HLaNb2O7 is presented here. A…

THEORETICAL INSIGHTS ON O2 AND CO ADSORPTION ON NEUTRAL AND POSITIVELY CHARGED GOLD CLUSTERS

With the aim of understanding the elementary steps governing the oxidation of CO catalyzed by dispersed or supported gold nanoclusters, the adsorption of molecular species, such as O2 and CO, on model neutral and positively charged clusters (Au(n)(m+) n = 1, 9, and 13; m = 0, 1, and 3) has been studied using an ab initio approach. The computed structural and thermodynamic data related to the binding process show that molecular oxygen interacts better with neutral clusters, acting as an electron acceptor, while CO more strongly binds to positively charged species, thus acting as an electron donor.

Synchrotron Radiation and Chemistry: Studies of Materials for Renewable Energy Sources

We present an overview of selected applications of synchrotron radiation methods to topical chemical research. The analysis is limited to the studies on materials for renewable energy sources, focussing on topics peculiar to chemical research, such as reactivity and synthesis routes; in particular, the paper takes into account subjects having some relevance for the production and storage of energy based on hydrogen. Hydrogen production and storage are taken into account in the sections concerning: (i) Dye-sensitized solar cells, (ii) Metal-organic frameworks and (iii) Hydrides for hydrogen storage; production of energy by fuel cell devices is treated in (iv) Oxide ion and proton conductors …

Crossing the boundary between fcc and hcp: the structure of nanosized cobalt is unraveled by a model of size distribution, shape and stacking faults allowing simulation of XRD, XANES and EXAFS

The properties of nanostructured cobalt in the fields of magnetic, catalytic and biomaterials depend critically on Co close-packing. In this paper we report a structural analysis of nanosized cobalt based on the whole XRD pattern simulation allowed by the Debye equation. The underlying structural model involves statistical sequences of cobalt layers and produces simulated XRD powder patterns bearing the concurrent signatures of hexagonal and cubic close packing. Size distribution, shape and distance distribution between pairs of atoms are also modelled. The simulation algorithm allows straightforward fitting to experimental data and hence the assessment of the model parameters. Analysis of …

Ultralow thermal conductivity in 1D and 2D imidazolium-based lead halide perovskites

Low-dimensional hybrid organic–inorganic metal halide perovskites are rapidly emerging as a fascinating sub-class of the three-dimensional parent structures, thanks to their appealing charge and thermal transport properties, paired to better chemical and thermal stabilities. Extensive investigations of the thermal behavior in these systems are of paramount relevance to understand their optoelectronic and thermoelectric applications. Herein, we present a complete thermophysical characterization of imidazolium lead iodide, (IMI)PbI3, a 1D pseudo-perovskite with chains of face-sharing octahedra, and histammonium lead iodide, (HIST)PbI4, a 2D layered perovskite with corner-sharing octahedra. Up…

Influence of SMSI effect on the catalytic activity of a Pt(1%)/ Ce0.6Zr0.4O2 catalyst: SAXS, XRD, XPS and TPR investigations

Abstract The steady-state activity of NO reduction by C3H6, in lean conditions, was studied on a Pt(1%)/Ce0.6Zr0.4O2 catalyst, in a plug-flow reactor, in the temperature range 100–500 °C. The influence of reductive pre-treatments on the catalytic performance at low temperature (250 °C) was investigated. Enhancement of the activity was found for the catalyst pre-treated in hydrogen at 350 °C as compared to the sample pre-treated in H2 at 800 and 1050 °C. Moreover, transient reactivity tests of NO reduction by hydrogen were also carried out. As previously observed, the sample reduced at 350 °C was the most active catalyst. In both types of reactions the temperature and the nature of pre-treat…

Treatment of grazing-incidence small-angle X-ray scattering data taken above the critical angle

The equations taking into account refraction at the sample surface in grazing-incidence small-angle X-ray scattering (GISAXS) when the angle between the incoming beam and the sample surface is slightly larger than the critical angle are derived and discussed. It is demonstrated that the refraction of both the incoming and the scattered beam at the sample surface affects the GISAXS pattern and that, when a planar bidimensional detector perpendicular to the incoming beam is used, the effect depends on the azimuthal detector angle. The smearing of the pattern depending on the size of the illuminated sample area in grazing incidence is estimated by simulations with Cauchy functions of different…

Structural and morphological rearrangements in quenched poly(ethylene) by simultaneous SAXS/WAXS

Structure formation by crystallization from the melt in a wide range of cooling rates (0.08-1 000°C/s) in low-density polyethylene has been studied by simultaneous small- and wide-angle X-ray scattering at the synchroton radiation source of DESY. The occurrence of two periodicities, characterized by different angular position of Bragg's maxima, was observed, pointing to the existence of two types of lamellar stacks, associated with two different long period values L 1 and L 2 (L 1 > L 2 ). L 1 depends on the cooling rate, whereas L 2 is almost constant. A comparison with isotactic polypropylene is performed, where a similar phenomenon takes place. While in the case of i-PP a definite correl…

Functionalization of a layered oxide with organic moieties: towards hybrid proton conductors

The design of innovative proton conductors for intermediate-temperature fuel cells, closing the gap between PEMFC and SOFC, is a forefront research theme in materials chemistry. [1] Layered perovskites with the Dion-Jacobson structure (ALaNb2O7) have bidimensional lanthanum niobate sheets, separated by a layer of A+ cations. These can be substituted by a variety of molecules with soft chemistry, to yield inorganic-organic hybrids. In particular, the intercalation of amines, alcohols, carboxylic or phosphonic acids, and their covalent binding to the sheets has been demonstrated recently. [2-4]We present preliminary results on the intercalation and covalent bonding of different organic molecu…

Solid–Solid Interfaces in Protonic Ceramic Devices: A Critical Review

The literature concerning protonic ceramic devices is critically reviewed focusing the reader's attention on the structure, composition, and phenomena taking place at solid-solid interfaces. These interfaces play a crucial role in the overall device performance, and the relevance of understanding the phenomena taking place at the interfaces for the further improvement of electrochemical protonic ceramic devices is therefore stressed. The grain boundaries and heterostructures in electrolytic membranes, the electrode-electrolyte contacts, and the interfaces within composite anode and cathode materials are all considered, with specific concern to advanced techniques of characterization and to …

A structural investigation is described of poly(L-lactic acid) by best fitting of powder X-ray diffraction patterns. The examined sample shows the already known pseudo-orthorhombic α-form, and it was possible to determine the location of the two 103 polymeric helices in the unit cell and the size distribution of the crystallites. Furthermore, a study is reported of the crystallization kinetics of the above cited polymer by light depolarization measurements in an optical microscope. The crystallization kinetic constants in bulk were evaluated in a temperature range (70–165°C) wider than that previously resulting from measurements of radial growth of spherulites.

Defect interaction and local structural distortions in Mg-doped LaGaO3: A combined experimental and theoretical study

A combined experimental and theoretical study of Mg-doped LaGaO3 electrolyte was carried out, with the aim to unveil the interaction between oxygen vacancy (Vo) and perovskite B site cations. LaGaO3 (LG) and LaGa0.875Mg0.125O2.938 (LGM0125) samples were comprehensively characterized by X-ray absorption spectroscopy (XAS) and X-ray diffraction, in order to investigate short- and long-range structures of both undoped and Mg-doped materials. XAS analysis evidenced a preferential Ga-Vo interaction in LGM0125, confirmed by periodic hybrid density functional theory calculations, which were combined with a symmetry-independent classes (SICs) approach in order to (a) obtain a detailed picture of th…

Toward a new hybrid proton conductor: lanthanum niobate layered perovskites as a source of tailorable surfaces

The modification of metal oxide surfaces with organic moieties has been widely studied as a method of preparing organic-inorganic hybrid materials for various applications. Among inorganic oxides, the ion-exchangeable layered perovskites [1], materials composed by perovskite-like slabs and intercalated cations, stimulated authors’ interest in reason of some encouraging electronic and reactive properties. In particular it is well known that the interlayer surface of such materials in their protonated form can be easily functionalized with organic groups (such as alcohols [2-3] or organophosphonic acids [4]) thus allowing the production of stable hybrid materials with new electronic and react…

A real-space approach to the analysis of stacking faults in close-packed metals: Modelling and Q-space feedback Longo Alessandro

An R-space approach to the simulation and fitting of a structural model to the experimental pair distribution function is described, to investigate the structural disorder (distance distribution and stacking faults) in close-packed metals. This is carried out by transferring the Debye function analysis into R space and simulating the low-angle and high-angle truncation for the evaluation of the relevant Fourier transform. The strengths and weaknesses of the R-space approach with respect to the usual Q-space approach are discussed.

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…

Characterisation of scheelite LaW0.16Nb0.84O4.08 ion conductor by combined synchrotron techniques: Structure, W oxidation state and interdiffusion

Abstract Scheelite-type materials such as LaNbO4 are increasingly attracting attention as a possible alternative to the most common fluorite and perovskite structure as ion conductors. However, they are much less used and investigated. The introduction of tungsten in lanthanum orthoniobate leads to conduction properties that are compatible with oxygen ion conductivity. In this paper, we studied the effect of the introduction of tungsten in the LaNbO4 structure. High resolution X-ray diffraction showed that in LaNb1-xWxO4+x/2 with x = 0.16 the monoclinic distortion is largely suppressed and the tetragonal phase is predominant at room temperature. By XANES/EXAFS we proved that tungsten is in …

Experimental observation of Electronic Metal support interaction: investigation of Au/Ceria catalysts by HERFD–XANES

In this paper we report the result of a recent experiment of high resolution XANES (HERFD-XANES) which evidenced this modification suggesting that gold clusters with very similar size can have a modified electronic structure (the empty d-Density-of-states) when they are deposited on ceria and titania oxide

Influence of metal–support interaction on the surface structure of gold nanoclusters deposited on native SiOx/Si substrates

The structure of small gold nanoclusters (R ~ 2.5 nm) deposited on different silica on silicon substrates is investigated using several characterization techniques (AFM, XRD, EXAFS and GISAXS). The grain morphology and the surface roughness of the deposited gold clusters are determined by AFM. The in-plane GISAXS intensity is modelled in order to obtain information about the cluster size and the characteristic length scale of the surface roughness. AFM and GISAXS results are in excellent agreement and show that the surface morphology of the deposited clusters depends on whether defect-rich (native) or defect-free (thermal) silica is used as a substrate. Gold clusters show a strong tendency …

The Role of the Local Atomic Order and Boundary Effects on the Electrical Transport of Ceria

Heavily acceptor doped ceria is a material of great relevance for applications in solid oxide fuel cells and oxygen membranes. Depending on the operation temperature, dopant concentration and microstructure (e.g. nanocrystalline vs. microcrystalline), the ionic transport properties of ceria can be mostly hindered by (i) grain boundaries or (ii) local atomic disorder in the bulk. Here, we present a selection of examples (ranging from thin films to ceramics) of how and to which extent these effects can affect the electrical transport properties. Emphasis will be given to the case of heavily doped nanocrystalline and microcrystalline ceria doped with samarium, erbium and ytterbium (dopant conc…

Catalytic and Electrical Properties of La1-xSrxCr1-yFeyO3-d as anodes for IT-SOFCs

A DFT investigation of CO oxidation over neutral and cationic gold clusters

Abstract The interaction of CO and O 2 with neutral and positively charged Au 9 and Au 13 clusters was studied using Density Functional Theory. The aim was the understanding of the elementary steps of the low temperature activity of supported gold nanoparticles towards carbon monoxide combustion, that is, the oxidation of CO to CO 2 in presence of dioxygen molecules. The adsorption of a single CO molecule gives rise to a substantial electronic rearrangement on both neutral and cationic gold clusters. On the contrary, the adsorption of dioxygen produces an electron transfer from neutral gold clusters to the O 2 , while the interaction with cationic Au nanoparticles is simply electrostatic. C…

Solid-state NMR characterization of the structure and thermal stability of hybrid organic-inorganic compounds based on a HLaNb2O7 Dion-Jacobson layered perovskite.

Dion-Jacobson phases, like MLaNb2O7, are an interesting class of ion-exchangeable layered perovskites possessing electronic and photocatalytic properties. Their protonated and organo-modified homologues, in particular, have already been indicated as promising catalysts. However, the structural analysis of these highly tailorable materials is still incomplete, and both the intercalation process and thermal stability of the included organic moieties are far from being completely understood. In this study, we present a thorough solid-state NMR characterization of HLaNb2O7·xH2O intercalated with different amounts of octylamine, or with decylamine. Samples were analyzed as prepared, and after th…

On the use of grazing-incidence small-angle X-ray scattering (GISAXS) in the morphological study of ion-implanted materials.

Grazing-incidence small-angle X-ray scattering has become a widely used technique for the morphological analysis of surface systems. Here it is show how this technique can be applied to a buried system, like metallic clusters in glass obtained by ion implantation. The optimization of the data-collection geometry is described as well as the details of the quantitative data analysis. An experimental example on Cu + Au-implanted glasses shows the potentiality of the technique.

Combined small-angle x-ray scattering/extended x-ray absorption fine structure study of coated Co nanoclusters in bis(2-ethylhexyl)sulfosuccinate

Chemically stable cobalt nanostructures have been prepared with Co(II) reduction in the confined space of cobalt bis(2-ethylhexyl)sulfosuccinate, Co(AOT)2, reverse micelles dispersed in n-heptane. The reaction was carried out by adding a solution of sodium borohydride in ethanol (1% weight) to a 0.2M micellar solution of Co(AOT)2 in n-heptane at a reductant to Co(II) molar ratio of 4. This procedure involves the rapid formation of surfactant-coated Co nanoparticles followed by their slow separation as nanostructures embedded in a sodium bis(2-ethylhexyl)sulfosuccinate matrix. The resulting composites, characterized by extended x-ray absorption fine structure and small-angle x-ray scattering…

Effects of redox treatments on the structural composition of a ceria–zirconia oxide for application in the three-way catalysis

Abstract The influence of calcination and redox cycles on the structural modification and redox properties of a ceria–zirconia mixed oxide of nominal composition Ce 0.6 Zr 0.4 O 2 were investigated by XRD and Rietveld refinement, by BET measurement, TPR and OSC analyses. The material is characterized by high total OSC and retains this property after several redox and calcination cycles up to 1273 K, despite the loss of porosity and the decrease of surface area. The Rietveld analysis of the diffractograms allowed to establish that at least two solid solutions are present in the as-prepared sample: a cubic phase, space group Fm-3m, richer in cerium compared to the nominal composition, a tetra…

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…

Structural analysis, phase stability and electrochemical characterization of Nb doped BaCe0.9Y0.1O3−x electrolyte for IT-SOFCs

Abstract To improve the chemical stability of high temperature proton conductors based on barium cerate, electrolyte powders doped with different amounts of niobium were synthesized by the citrate–nitrate auto-combustion method. Pure single phases of BaCe 0.9− x Nb x Y 0.1 O 3− x (BCYN, 0.03 ≤  x  ≤ 0.12) were obtained by thermal treatment at 1000 °C. Sintering at 1450 °C for 10 h produced dense pellets. X-ray absorption spectroscopy allowed to define the dopant ion insertion site and the co-dopant valency. Treatments in pure CO 2 atmosphere at 700 °C for 3 h and subsequent XRD analysis were carried out to probe the chemical stability of the produced electrolytes. The influence of the prese…

Cation Diffusion and Segregation at the Interface between Samarium-Doped Ceria and LSCF or LSFCu Cathodes Investigated with X-ray Microspectroscopy

The chemical compatibility between electrolytes and electrodes is an extremely important aspect governing the overall impedance of solid-oxide cells. Because these devices work at elevated temperatures, they are especially prone to cation interdiffusion between the cell components, possibly resulting in secondary insulating phases. In this work, we applied X-ray microspectroscopy to study the interface between a samarium-doped ceria (SDC) electrolyte and lanthanum ferrite cathodes (La0.4Sr0.6Fe0.8Cu0.2O3(LSFCu); La0.9Sr0.1Fe0.85Co0.15O3(LSCF)), at a submicrometric level. This technique allows to combine the information about the diffusion profiles of cations on the scale of several micromet…

Structural Characterization of Surfactant-Coated Bimetallic Cobalt/Nickel Nanoclusters by XPS, EXAFS, WAXS, and SAXS

Cobalt nickel bimetallic nanoparticles were synthesized by changing the sequence of the chemical reduction of Co(II) and Ni(II) ions confined in the core of bis(2-ethylhexyl)phosphate (2)., and Ni(DEHP)(2). The reduction was carried out by mixing, sequentially or contemporaneously, fixed amounts of n-heptane solution of Co(DEHP)2 and Ni(DEHP)2 micelles with a solution of sodium borohydride in ethanol at a fixed (reductant)/(total metal) molar ratio. This procedure involves the rapid formation of surfactant-coated nanoparticles, indicated as Co/Ni (Co after Ni), Ni/Co (Ni after Co), and Co + Ni (simultaneous), followed by their slow separation as nanostructures embedded in a sodium bis(2-eth…

Palladium local structure of La1-xSrxCo1-yFey-0.03Pd0.03O3-δperovskites synthesized using a one pot citrate method

Nanostructured La1-xSrxCo1-yFey-0.03Pd0.03O3-δ(LSCF-Pd) perovskites with fixed La-Sr composition (x = 0.4) and two different Fe contents (y = 0.2 and 0.8) were successfully synthesized using a one pot citrate method starting from nitrates of the metal cations. Pd-free La1-xSrxCo1-yFeyO3-δ(LSCF) systems were prepared for comparison. LSCF powders were calcined at 1300 °C and characterized by XRD and Rietveld refinement, EXAFS, XPS, TPR analyses. Promotion of La0.6Sr0.4Co0.8Fe0.2O3-δand of La0.6Sr0.4Co0.2Fe0.8O3-δby incorporation of palladium was evidenced by solving the local environment of Pd using EXAFS spectroscopy. XPS analyses, in agreement with TPR measurements, demonstrated an inc…

In situ X-ray absorption spectroscopy: evidence of Strong Metal Support Interaction (SMSI) in Pt ceria-zirconia catalysts

SAXS/WAXS study of the annealing process in quenched samples of isotactic poly(propylene)

The structural rearrangement in samples of quenched isotactic poly(propylene) (iPP) submitted to different annealing treatments has been studied using simultaneous small- and wide-angle X-ray scattering (SAXS/WAXS) at the synchrotron radiation source of DESY, Hamburg. From a quantitative analysis of the WAXS profiles the values of the α-monoclinic, mesomorphic, and amorphous mass fractions coexisting in the material were determined. It is demonstrated that the SAXS patterns were characterized by two different long-period values that are attributed to α- and mesomorphic periodicity, respectively. The related α- and mesomorphic volume phase fractions, calculated from the analysis of the SAXS …

Synthesis and structural analysis of novel proton conductors RE1-xBa1+xGaO4-x/2 (RE = La, Nd)

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