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Trigonal-prismatic coordinated transition metal dichalcogenides (TMDCs) are formed from stacked (chalcogen)–(transition metal)–(chalcogen) triple layers, where the chemical bond is covalent within the triple layers and van der Waals (vdW) forces are effective between the layers. Bonding is at the origin of the great interest in these compounds, which are used as 2D materials in applications such as catalysis, electronics, photoelectronics, sensors, batteries and thermoelectricity. This paper addresses the issue of modelling the structural disorder in multilayer TMDCs. The structural model takes into account stacking faults, correlated displacement of atoms and average crystallite size/shape, and is assessed by simulation of the X-ray diffraction pattern and fitting to the experimental data relative to a powdered sample of MoS2 exfoliated and restacked via lithiation. From fitting, an average crystallite size of about 50 Å, nearly spherical crystallites and a definite probability of deviation from the fully eclipsed atomic arrangement present in the ordered structure are determined. The increased interlayer distance and correlated intralayer and interlayer atomic displacement are attributed to the presence of lithium intercalated in the vdW gap between triple layers (Li/Mo molar ratio of about 0.06). The model holds for the whole class of trigonal-prismatic coordinated TMDCs, and is suitably flexible to take into account different preparation routes.

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 partially charged. The dynamism of the gold electronic configuration was evidenced by a temporary variation of the gold d-orbital population during the oxidation reaction. The interpretation of X-ray spectroscopy data is supported by ab initio simulations performed using the FDMNES code.

Layered TiS

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 (C14H19N2)PbIBr2 crystal phases were successfully synthetized and do not show segregation effects. TGA and DSC measurements showed that, while all these materials are stable up to 250 degrees C, the iodine-rich (C14H19N2)PbI3 and (C14H19N2)PbI2Br species undergo an irreversible phase transition around 220 degrees C to a high-temperature phase, with a smaller molar volume and an apparent symmetry lowering (to orthorhombic Pca2(1)). In these two cases, variable-temperature X-ray diffraction measurements showed a substantial crystal-to-crystal transformation, without intermediate melting or amorphization. The thermal expansion coefficients of (C14H19N2)PbI3 and (C14H19N2)PbBr3 are highly anisotropic and on the order of 10(-4) K-1 along the b crystallographic axis. Microscopic and spectroscopic measurements were performed to complement the structural analysis of the samples: band gaps in the near UV range (3.3 and 3.8 eV for (C14H19N2)PbI3 and (C14H19N2)PbBr3, respectively) were obtained.

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 computational modeling by ab initio approaches. An outlook about future developments and improvements highlights the necessity of a deeper insight into the advanced analysis of what happens at the solid-solid interfaces and of in situ/operando investigations that are presently sporadic in the literature on protonic ceramic devices.

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.

The structures of the disordered 1D (pseudo-)perovskites of general TMSO(Pb

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+ vacancies, and interstitial iodide) to consider electrical neutrality. Both the formation energy evaluation and the structural parameters after relaxation are in very good agreement with available experimental data (both X-ray diffraction and absorption spectroscopy), confirming that Pb2+ vacancies are indeed the primary ionic charge-compensation mechanism leading to solid solutions described by the formula ((CH3)3SO)3Pb3xBi2(1-x)V(1-x)I9 (0 < x < 1), where V indicates a B site vacancy. As a consequence of the complete miscibility, the defect concentration at intermediate compositions is considerable, and it is probably responsible for various peculiar structural effects observed, e.g., in ((CH3)3SO)3Pb0.99Bi1.34I9, which are related to short-range order phenomena in the chain composition. Atomistic simulations were then carried out to estimate defect-defect interactions as a function of their respective positions inside the linear PbI6/BiI6 octahedral chains. The resulting bond energies for atom pairs and triads effectively explain the relative stability of defect clusters. This approach is expected to shed light on the short-range order in this class of doped materials, but it can be extended to other structures as well. The understanding of defect structures and control of structural and electronic properties have implications for the engineering of doped materials, which find vast applications in optoelectronic devices.

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.

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 diffraction analysis indicates that the use of DMF/DMSO mixed solvents promotes the strengthening of a dominant 100 or 210 texturing, as compared the case of pure DMF, and that the haloplumbate chains always lie in a plane parallel to the substrate. Under specific DMF/DMSO solvent volume ratios, the prepared films are found to be highly stable in time (up to seven months under fluxing N2 and in the dark) and to highly moist conditions (up to 25 days at 78% relative humidity). Furthermore, for representative (PRSH)PbX3 films, resistance against ultraviolet exposure (λ = 380 nm) is investigated, showing complete stability after irradiation for up to 15 h at a power density of 600 mW/cm2. These results make such thin films interesting for highly stable perovskite-based (opto)electronic devices.

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.

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 are further supported by in situ X-ray Raman spectroscopy (YRS) that allowed us to monitor the temperature evolution of the 0 Kedge. XRS evidences that nickel-doped LSCF shows unmodified O2p-TM3d density of states, which proves that the Co oxidation state is preserved. Electrochemical impedance spectroscopy measurements were carried out over half-cell systems consisting of LSCF-based materials deposited onto a Ce0.8Gd0.2O2-delta electrolyte. The improvement of the electrochemical performances of the Ni-doped La0.6Sr0.4Co0.2Fe0.8-0.03Ni0.03O3-delta sample with respect to a reference Ni-impregnated LSCF is attributed to the stabilisation of the TM-O-6 structural units, which were recently proposed as the functional units for oxygen reduction.

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 generally very good agreement with the available experimental data is found in reproducing both structural features and C-13-NMR chemical shifts, and marked differences between the two considered intercalated compounds are evidenced, with possible important outcomes for proton conduction. Notably, the free imidazole molecules are easily protonated by the acidic protons present in the interlayer spacing, thus inhibiting an efficient charge transport mechanism. In order to overcome this problem, a model system has been considered, where the imidazoles are bound to the end of a butyl chain, the whole being intercalated between two perovskite layers. The obtained theoretical data suggest that, in such a system, proton transfer between two adjacent imidazoles is a barrierless process. These results could then open new perspectives for such hybrid proton conductors.

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.

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, C and applied electrical bias ranging from +1 V to &minus, 1 V in air). The in situ XAS measurements allowed us to follow the LSCF degradation into simple oxides. The rapid deterioration of LSCF is ascribed to the formation of excess of oxygen vacancies leading to the collapse of the mixed perovskite structure.

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.

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 time to the study of materials for energy, and it is proposed as a useful structural tool, complementary to electrochemical characterization, for the investigation of the compatibility between materials for SOFCs. We demonstrate that an impressive calcium drift towards the LSM cathode takes place: the dopant is depleted throughout a region of LNC several micrometers wide, causing a decrease of charge carriers in the electrolyte and eventually impairing its conductivity. This poses a significant challenge for evaluating electrolyte/electrode couples in proton-conducting SOFCs based on LNC.

A combined experimental and theoretical study of Mg-doped LaGaO

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 micrometers, together with the chemical information coming from space-resolved X-ray absorption spectroscopy. In SDC-LSCF bilayers, we find that the prolonged thermal treatments at 1150 °C bring about the segregation of samarium and iron in micrometer-sized perovskite domains. In both SDC-LSCF and SDC-LSFCu bilayers, cerium diffuses into the cathode perovskite lattice A-site as a reduced Ce3+cation, whereas La3+is easily incorporated in the ceria lattice, reaching 30 atom % in the ceria layer in contact with LSFCu.

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 materials are discussed.

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 assessment of the model parameters. Analysis of two samples having, respectively, h.c.p. and f.c.c. appearance is reported. Extended X-ray absorption fine-structure (EXAFS) and X-ray absorption near-edge structure (XANES) spectra are simulated on the basis of the model, giving a tool for the interpretation of structural data complementary to XRD. The outlined structural analysis provides a rigorous structural basis for correlations with magnetic and catalytic properties and an experimental reference forab initiomodelling of these properties.

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 thermal treatment at different temperatures up to 220 °C. The substitution of pristine proton ions was followed via(1)H MAS NMR spectroscopy, whereas the alkyl chains were monitored through (13)C((1)H) CP MAS experiments. The interactions in the interlayer space were explored using (13)C((1)H) 2D heteronuclear correlation experiments. We demonstrate that some of the protons are involved in the functionalization reaction, and some of them are in close proximity to the alkyl ammonium chains. Heating of the hybrid materials leads first to a rearrangement of the alkyl chains and then to their degradation. The spatial arrangement of the chains, their interactions and the thermal behavior of the materials depend on the extent of the functionalization, and on the nature of the intercalated alkyl ammonium ions.

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 increase of superficial oxygen vacancies, the variation being much more pronounced in the La0.6Sr0.4Co0.8Fe0.17Pd0.03O3-δsample. It is argued that this increase is associated with the introduction of Pd in the B site of LSCF. Moreover, ionic Pd4+was detected as the only palladium species on the perovskite surface, whereas Pd metal clusters of about 2 nm, not detectable in the surface, are embedded in the matrix and strongly interact with the bulk. This result has strong consequences in the synthesis and in the design of new perovskite materials that can be used as cathodes in fuel cell application at intermediate operating temperatures. © the Partner Organisations 2014.

Ce0.8Sm0.2O2Â−Âxpowders 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 atmosphere (4% H2/Ar), and Ce0.8Sm0.2O2Â−Âxprepared with sucrose showed, at scanning electron microscopy images, the highest average grain size. Impedance spectroscopy experiments in air disclosed different grain boundary resistances on the basis of synthesis fuel employed and, in particular, Ce0.8Sm0.2O2Â−Âxprepared with sucrose exhibited the best electrical performance. Solution combustion synthesis thereby was able to tailor the morphological and reduction properties of Ce0.8Sm0.2O2Â−Âxpowders affecting even the microstructure of sintered pellet.

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 independently of methane concentration. The H2S influence on methane oxidation was evaluated and experiments in CH4/H2S gas mixture indicated that La0.9Sr0.1Cr0.7Fe0.3O3−δ oxidized CH4 to CO2 and CO, as well as H2S to SO2. La0.9Sr0.1Cr0.7Fe0.3O3−δ was therefore identified a potential anode material for intermediate temperature solid oxide fuel cells directly fed with CH4 in the presence of H2S.

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 gold atoms placed at the interface between Au and ceria.

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.

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 of local deviation from the cubic arystotype even if undoped, which upon substitution by the perceptibly larger Y3+, playing the role of a rigid inclusion, is further increased. This distortion is one limiting factor concerning the Y3+ solubility. The effects are correlated to the proton conduction properties of BZY.

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 deepen new interpretations, concerning experimental findings already reported in the literature. In particular, the bimodal distribution characterizing the Y-O first coordination shell, found by EXAFS analysis, could be attributed to a local clustering of Y atoms showing characteristic Y-O-Y arrangements. Moreover, the local charge analysis, characterizing the models containing or not hydrogen atoms, showed that the moving protons are able to dynamically change the properties of their near environment, in any case, leaving unaltered the global protonic conduction features of the material, irrespective of the kind of cation in a given Z-O-Ξ moiety.

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 intertetrahedral hydrogen bonds is formed, producing a contraction of the a axis. On the basis of thermogravimetric analysis, EXAFS, XRD and infrared spectroscopy (IR) results, we propose that the stiffness of the GaO4 tetrahedra hinders the intratetrahedral proton transfer, while the noticeable fraction of protons involved in strong hydrogen bonds limit the proton reorientational freedom.

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 solid solution, prevents any CeAlO 3 formation. On the contrary, such phase due to the interaction between Ce 3+ and the alumina present in the washcoat is detected when redox cycles are carried out on the ceria–zirconia metal free. Transmission electron microscopy (TEM) investigations of the redox cycled Pt/ceria–zirconia/alumina catalyst detected ceria–zirconia grains with diameter between 10 and 35 nm along with highly dispersed Pt particles (2–3 nm) strongly interacting with ceria. Scanning electron microscopy (SEM) and EDX analyses, recorded on the redox cycled Pt/ceria–zirconia/alumina washcoated monolith evidence a homogeneous distribution of the active components through the channels even after redox aging. Reduction behaviour and CO oxidation activity are in good agreement with the structural modification of the solid solution induced by the redox cycles and reflect the positive effect of Pt/ceria interaction on the catalytic performances. The effect of redox aging on the NO reduction by C 3 H 6 , in lean conditions, was investigated over the Pt/ceria–zirconia/alumina monolith. The catalyst shows at low temperature (290 °C) good NO removal activity and appreciable selectivity to N 2 .

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 adsorbates does not take place. Only the latter mechanism on positively charged Au13 cluster can give rise to the rupture of dioxygen and carbon dioxide formation. Detailed reaction paths corresponding to this case are calculated.

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 spectra were fitted on the basis of f.c.c. and noncrystalline arrangements. The best results were obtained by the f.c.c. motif, while a simulation consisting in the superposition of f.c.c. and noncrystalline components in the relative amounts determined by XRD analysis gave a poor agreement with the experimental data. It was concluded that the good XRD fitting obtained by linear combination of lognormal size-distributed f.c.c. cuboctahedral, decahedral and icosahedral contributions was a result of the flexibility of the basis set of functions, but that the complementary analysis of X-ray absorption data did not confirm the presence of a noteworthy fraction of noncrystalline particles.

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 increasing with dopant amount. For a dopant concentration estimated as x > 0.17, a poorly crystallized yttrium oxide phase that cannot be detected by X-ray diffraction is segregated. The static disorder around Y noticeably increases in the protonated samples and can be related to a preferential location of protons near the dopant.

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.

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.

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 with a typical correlation length of about 86 A and an intercluster Bragg distance of 37 A, quite different from the values of commercial film. Observation on the swelling of the films revealed that the semi-crystalline structure, once soaked in water, swells less than the ionomeric part, leading to an unusual small-angle X-ray scattering (SAXS) profile in which the matrix and the ionomer peak are significantly overlapped. The ionic conductivity measured at T = 80 °C shows slightly higher values for the re-cast Nafion membrane. A power density of about 0.490 W cm−2 at 0.6 V and at T = 80 °C in humidified hydrogen/air was obtained for the developed membrane.

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 observed. For increasing values of x/1−x in the solid solution Ce1−xLaxO2−x/2, the Ce–O distance decreases, while La–O distance remains nearly constant.

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 tetragonal phase (t′) richer in zirconium. The first redox treatment modifies the composition towards two different solid solutions with composition closer to the nominal one: a cubic Ce 0.65 Zr 0.35 O 2 and a tetragonal (t′) Ce 0.47 Zr 0.53 O 2 . No changes are noticed after four further redox cycles, while the successive calcination at 1273 K gives rise to a second cubic phase richer in cerium and to another tetragonal phase richer in zirconium. Noteworthy a further redox cycle reorganizes the sample to a similar situation as before the calcination treatment and this configuration is maintained for four redox cycles. This alternance is restored after calcination and successive four redox cycles. The total OSC measured after the above treatments is high and increases after the successive cycles.

Ceria-zirconia mixed oxides of nominal composition Ce0.6Zr0.4O2 were prepared by sol-gel method. The structural and morphological modifications of these materials due to calcination and redox treatments up to 1000°C were studied by X-ray diffraction (XRD) and Rietveld refinements, specific surface area measurements (BET), oxygen storage capacity (OSC), TEM and SEM analyses. The materials maintain high OSC after several hours of treatments at 1000°C in oxidizing and reducing atmosphere, showing good resistance to the thermal ageing. An improvement of the OSC is manifested after repetitive redox cycles, even though textural characterization shows that reduction/oxidation processes induce sintering of the crystallites.

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 the different Mg and Vo configurations in the doped material and (b) characterize the structural features of the conducting sites. Among the 28 structures of LGM0125 considered in the SIC approach, the Ga-Vo-Ga and Ga-Vo-Mg axial configurations (oriented along the b crystallographic axis) were found to be the most stable. The relative stability of all vacancy configurations considered could be related to geometric distortions of the B-sites, possibly significantly affecting the oxygen-ion diffusion process in such electrolytes.

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 further clarified and a new tetragonal space group is proposed for this compound, better reproducing the experimental cell parameters and yielding to a more realistic picture of the system. The electronic investigation highlighted that all the compounds considered are very similar to each other and that the interaction between interlayer cations and perovskite slabs is purely ionic, except for the proton that is, instead, covalently bound.

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 cristobalite. SAXS measurements, using the classical method based on Porod's law, yielded the total surface area of the systems. The calculated areas were compared with the surface areas determined by the nitrogen adsorption technique using the analytical method of Brunauer–Emmett–Teller. The results are explained in terms of sizes of the alkali ions and cell volume of the different crystalline phases.

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.

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 mixtures of pretreated Pd and Ag monometallic samples were tested. The structural data (XRD, XPS, EXAFS) along with the catalytic results would indicate that Ag 0 and Pd 0 species are the catalytic sites acting with certain synergism.

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 dilute (volume fraction of clusters greater than or equal to 0.01) and very thin (50 nm) systems. In the presented experiment, both pure and alloy clusters in the nanometer range of size were observed to form, pointing out the complexity of the cluster formation process in terms of physical and chemical driving forces.