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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, niobium and lanthanum were probed with space-resolved X-ray absorption spectroscopy. The ab initio modeling of the near-edge X-ray absorption spectra reveal that the cation interdiffusion is facilitated by the structural flexibility of the perovskite structure, which is able to accommodate a variety of foreign cations in different oxidation states. Limited stability at high-temperatures was found for all candidate perovskite compositions in contact with lanthanum niobate. (C) 2021 Elsevier Ltd. All rights reserved.

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 different Pb2+/Bi3+ ratios between (TMSO)PbI3 and (TMSO)3Bi2I9, and two for the bromide counterparts, were synthetized. Due to the charge compensation mechanism, these systems are best described by the (TMSO)3Pb3xBi2(1-x)I9 (x = 0.98, 0.92, 0.89, 0.56, and 0.33) and (TMSO)3Pb3xBi2(1-x)Br9 (x = 0.83 and 0.37) formulae. X-ray powder diffraction (XRPD) measurements were employed to determine the crystal structure of all studied species and further used to test the metal cation miscibility within monophasic samples not showing cation segregation. These systems can be described through an ionic defectivity on the pseudo-perovskite B site, where the Pb2+/Bi3+ replacement is compensated by one Pb2+ vacancy for every Bi3+ pair. This leads to a wide range of possible different (numerical and geometrical) chain configurations, leading to the unique features observed in XRPD patterns. The optical band gap of the iodide samples falls in the 2.11-2.74 eV range and decreases upon increasing the Bi3+ content. Interestingly, even a very low loading of Bi3+ (1%) is sufficient to reduce the band gap substantially from 2.74 to 2.25 eV. Periodic density functional theory (DFT) calculations were used to simulate the atomic and electronic structures of our samples, with predicted band gap trends in good agreement with the experimental ones. This work highlights the structural flexibility of such systems and accurately interprets the ionic defectivity of the different pseudo-perovskite structures.

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 materials show the highest proton uptake.

In this work we followed the formation of palladium nanoparticles, starting from palladium (II) acetate precursor, inside a poly(4-vinylpyridine-co-divinylbenzene) polymer in presence of different reducing agents. The formation and growth of palladium nanoparticles in presence of H-2 was followed as a function of temperature by simultaneous XANES-SAXS techniques, coupled with DRIFT spectroscopy in operando conditions. It was found that the pyridyl functional groups in the polymer plays a fundamental role in the stabilization of the palladium (II) acetate precursor, as well as in the stabilization of the palladium nanoparticles. The effect of a thermal treatment in alcohol (ethanol and 2-propanol) was preliminarily investigated by means of DRIFT spectroscopy in operando conditions. We found that alcohols act as reducing agents for Pd(OAc)(2). The obtained palladium nanoparticles were preliminarily characterized by means of IR spectroscopy using CO as probe molecule. (C) 2016 Elsevier B.V. All rights reserved.

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 concentration profiles show striking reactive phenomena at the interface with a variety of micrometer-sized secondary phases: In particular, X-ray absorption spectra reveal at least three different chemical states for manganese (from +3 to +6). Also in LSM/SDC, a couple previously reported as chemically stable, we found the formation of small islets of SmMnO3 after the migration of manganese to the SDC side; these may constitute the nuclei for the subsequent formation of an interfacial resistive layer after more prolonged operation. The ability of manganese to adopt several oxidation states and crystal chemical environments is indicated as a possible cause for these behaviors.

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 its 6+ valence state and no W5+ was detected. With X-ray microspectroscopy, we studied in detail with a submicrometre-probe the interdiffusion and degradation processes taking place between the material and LSM, a common electrode material, during their long-term contact at high temperatures.

International audience; Simultaneous time-resolved SAXS and XANES techniques were employed to follow in situ the formation of Pd nanoparticles from palladium acetate precursor in two porous polymeric supports: polystyrene (PS) and poly(4-vinyl-pyridine) (P4VP). In this study we have investigated the effect of the use of different reducing agents (H-2 and CO) from the gas phase. These results, in conjunction with data obtained by diffuse reflectance IR (DRIFT) spectroscopy and TEM measurements, allowed us to unravel the different roles played by gaseous H-2 and CO in the formation of the Pd nanoparticles for both PS and P4VP hosting scaffolds

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 and in (v) Electrodes for fuel cells. These arguments allowed to give a coherent outline of the involvement of synchrotron radiation techniques in traditional branches of chemistry such as inorganic and organic chemistry, catalysis and electrochemistry.

The reactivity of palladium acetate inside a poly(4-vinylpyridine-co-divinylbenzene) polymer is strongly influenced by the establishment of interaction between the Pd precursor and the pyridyl functional group in the polymer. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and simultaneous X-ray absorption near edge structure (XANES) and small angle X-ray scattering (SAXS) techniques have been applied to monitor the reactivity of palladium acetate in the presence of H-2 and CO as a function of temperature. H-2 reduces palladium acetate to Pd nanoparticles and acetic acid. The pyridyl groups in the polymer play a vital role both in stabilizing the formed acetic acid, thus allowing its detection by means of DRIFTS, and the final Pd nanoparticles, which are extremely small and mono-dispersed. On the contrary, CO does not reduce palladium acetate. Rather, it forms Pd2+ carbonyl adducts, which favor the detachment of the acetate ligands and their thermal degradation. These adducts are well observable by means of SAXS because they cause an important local change of the electronic density.

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. This does not depend on the long-range symmetry that is revealed by X-ray diffraction studies. From the similarity of the DOS of α-Bi2O3 and Ta-doped bismuth oxide, it is inferred that the force governing the local coordination of Bi is essentially the same in all forms of Bi2O3. As the local Bi environment, determined by X-ray absorption spectroscopy, is also found to be very similar in all investigated samples, regardless of the dopant concentration, the local mechanism of oxide ion diffusion is arguably similar in doped and undoped bismuth oxide.

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 hydroxyls around the dopant in the Y-doped BaCeO3 compounds.

Simultaneous time-resolved SAXS and XANES techniques were employed to follow in situ the formation of Pd nanoparticles in a porous polystyrene support, using palladium acetate as a precursor and gaseous H2 or CO as reducing agents. These results, in conjunction with data obtained by diffuse reflectance UV–vis and DRIFT spectroscopy and TEM measurements, allowed unraveling of the different roles played by gaseous H2 and CO in the formation of the Pd nanoparticles. In particular, it was found that the reducing agent affects (i) the reduction rate (which is faster in the presence of CO) and (ii) the properties of the hosted nanoparticles, in terms of size (bigger with CO), morphology (spherical with H2, triangular-like with CO), and surface properties (unclean with CO). The importance of a multitechnique approach in following the whole process of metal nanoparticles formation clearly emerges.

The effect of pre-reduction in solution with chemical reagents on the catalytic performance and catalyst properties of Pd/carbon catalysts was systematically investigated with a multitechnique approach. The results are critically discussed in comparison to those recently obtained on analogous Pd/alumina catalysts. It was proved that the Pd phase on the carbon surface is characterized by a high mobility, opposite to what occurs on alumina. As a result, the Pd particles on carbon aggregate together during pre-reduction, with a consequent decrease in available metal surface. Pd particles remain aggregated also in reaction conditions; the decreased Pd dispersion negatively affects the catalyst activity in the debenzylation of 4-benzyloxyphenol.

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-ethylhexyl)phosphate matrix. The resulting composites, together with those obtained by reducing the n-heptane solutions of pure Co(DEHP)(2) or Ni(DEHP)(2), were characterized by XPS, EXAFS, WAXS, and SAXS. The data analysis confirms the presence of nanometer-sized surfactant-coated cobalt, nickel, and cobalt/nickel particles. As expected, the composition and internal structure of cobalt/nickel bimetallic nanoparticles are influenced by the preparation sequence as well as by the "chemical affinity" between the surfactant and the metal. However, some atomic-scale physicochemical processes play a subtle role in determining the structural features of bimetallic nanoparticles. Further effects due to the competition between nanoparticle growing process and surfactant adsorption at the nanoparticle surface were observed.

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, showing a strong interaction of Gd3+ with positively charged defects. The environment of gadolinium is compared with the previously investigated local structure of dopants in Y:BaCeO3 and In:BaCeO3. It is observed that yttrium and gadolinium, which induce higher proton conductivity, are characterized by low solubility and strong interaction with positive defects; on the contrary, the lower proton conductivity of In:BaCeO3 coexists with full dopant solubility and insignificant interaction with oxygen vacancies and hydroxyls. A comprehensive interpretation of this behavior is proposed, in terms of a different dopant-host oxide interaction.

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, showed the presence of subnanometer sized cobalt nanoparticles aggregated together to form elongated structures coated by the surfactant molecules.

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 structural rearrangement of the hydrated solid.

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 673 K) allows to conclude that the anharmonicity of In-O thermal motion is about 1 order of magnitude lower than in other perovskites with higher proton conductivity. It is argued that the lower proton diffusivity displayed by In:BuZrO3 depends on (a) proton trapping at the dopant site due to the formation of a stable O-H center dot center dot center dot O hydrogen bond; (b) reduced anharmonicity of the M-O vibrations; (c) different strength of O-H bonds originated by electronic density rearrangement.