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 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

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 structure are still matter of debate. The kind of trivalent dopant and its size, and the doping level, have all been found to critically influence the conductivity: to date, however, no comprehensive model was developed, and no clear explanations exist between the chemical and dynamical properties. Here we present results collected in several EXAFS experiments on doped BaCeO3 and BaZrO3 spanning three years, on the Ba site, Ce site, and the dopant (yttrium, gadolinium, indium: the ionic sizes of these are respectively equal, larger and smaller than Ce4+) site. The local structures up to about 6 Å around each site are solved with state-of-the-art techniques employing both the GNXAS and FEFF approaches, revealing unique features and demonstrating that in this case the conventional diffraction techniques are not suited to unravel the complexity of doped crystals. In particular, the attention will be drawn on the local deviations from Vegard’s law, the local expansion/contraction as a function of hydration degree, the interplay between dopant and defects, and the chemical compatibility (Pearson absolute hardness) instead of ionic size matching. The EXAFS results are correlated with complementary information about the dynamics of protons and other defects (IR and neutron vibrational spectroscopy, QENS, ionic and electronic conductivity measurements)

STRUCTURAL PROPERTIES DETERMINING THE NEAR-EDGE X-RAY ABSORPTION SPECTRA OF LEAD HALIDE PEROVSKITES

X-ray absorption spectroscopy (XAS) is an excellent complement to diffraction techniques for studying the structure of materials. Despite the extensive research on lead halide perovskites for optoelectronic applications, the application of XAS to these materials has been relatively limited and yielded varying degrees of success. In order to develop generalizable approaches for analyzing XAS spectra of halide perovskites with different compositions, we conducted an experimental and computational study on a hybrid Pb/Bi iodide solid solution, serving as a model system. The monodimensional lead halide “perovskite” (TMSO)3Pb3xBi2(1-x)I9 [1] exhibits correlated disorder at the metal cation site, resulting in various possible arrangements of Pb, Bi, and metal vacancies (Figure 1). Through simulations, we observed that the X-ray absorption near-edge structure spectra (at the Pb, Bi, and I X-ray absorption edges) show some sensitive to these alternations. Surprisingly, we discovered that the cation spectra can be explained by simple distortions of independent PbI6/BiI6 octahedral units, without considering long-range multiple scattering contributions that typically dominate the near-edge region.[2] This finding enables the prediction and modeling of X-ray absorption near-edge spectra using simple structural units, suggesting that similar approaches can be successfully extended to other halide perovskites in the future

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 BaCeO3, thus involving limited carrier concentration. Perovskites are affected by different drawbacks: barium cerate compounds are very sensitive to the acidic components present in the environment and in particular to CO2 that induces decomposition in barium carbonate and cerium oxide; barium zirconate, notwithstanding a very high bulk conductivity, is biased by high grain boundary resistivity. A possible alternative to perovskite-like compounds is constituted by fergusonite-type lanthanum niobate and lanthanum tantalate compounds, characterized by a tetrahedral coordination of Nb and Ta. These oxides present a very high chemical stability but very low carrier concentration, usually induced by Ca-doping the lanthanum site [1]. Among the different trivalent dopants, it was demonstrated by X-ray absorption spectroscopy that indium is able to enter in any composition in the perovskite network, thus providing a very high carrier concentration, even if with lower proton mobility. This property of indium was ascribed to its electronic structure and in particular to the low Pearson hardness, allowing this cation to fit in a hosting matrix with the least structural strain [2]. A preliminar attempt of exploiting indium for enhancing the carrier concentration of lanthanum niobate was carried out. The solid state synthesis involved amounts of the reactant simple oxides suitable to force indium doping of the niobium site. X-ray diffraction do not show significant amounts of secondary oxide phases

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 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

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 molecules, in order to develop hybrid proton conductors for use in intermediate temperature fuel cells. Smaller molecules (such as alcohols) are intercalated to expand the interlayer space, to form intermediates for the further binding of proton carriers such as imidazoles or sulfonates.The intercalation process is investigated by XRD (to measure the interlayer distance) and TGA (to determine the weight loss upon thermal decomposition). NMR is applied to confirm the covalent bonding between the organic and oxide parts. The intercalation behavior of different functional groups is explained in terms of van der Waals and/or hydrogen bonding between organic chains. The interplay of theory (ab initio and periodic DFT) and experiment allowed us to elucidate the 1H and 13C-NMR spectra, and to investigate the nature of interaction (i.e. ionic or covalent bond) of the organic chains with the interlayer surface

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-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

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 12inorganic) iodide and bromide pseudo-perovskites (ABX3) containing the trimethylsulfoxonium cation (CH3)3SO+ (TMSO) in the A site, Pb/Bi in the Bsite, 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 facesharing [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 12 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 12x)I9 (x = 0.98, 0.92, 0.89, 0.56, and 0.33) and (TMSO)3Pb3xBi2(1 12x)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 2.11 122.74 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