Disorder in La1-xBa1+xGaO4-x/2 ionic conductor: resolving Pair Distribution Function through inside from first principles modeling

Ionic conduction in dry LaBaGaO4 occurs through the vacant oxygen sites formed by the substitution of Ba for La. The resulting La1 12xBa1+xGaO4 12x/2 solid solution shows significant disorder characteristics. The local structure of compositions x = 0, 0.20 and 0.30 was studied using the pair distribution function (PDF). Unfortunately, increasing peak overlap and the number of independent structural parameters make PDF modeling challenging when dealing with low-symmetry phases. To overcome this problem, density functional theory (DFT) was employed to create different structural models, each one with a different relative position for the substitutional Ba ion with respect to the oxygen vacancy. The atomic distributions generated by DFT were used as a starting point to refine experimental PDF data. All models result in the formation of Ga2O7 dimers, with their major axis oriented along the c axis. At the local scale, the most stable DFT model also provides the best fit of the PDF. This accounts for the dopant as first and second neighbors of the vacancy and of the O bridge in the dimer, suggesting that substitutional barium ions act as pinning centers for oxygen vacancies. Above 6 \uc5 the average orthorhombic structure fits the PDF better than the DFT models, thus indicating that Ga2O7 dimers are not correlated with each other to form extended ordered structures. The combination of DFT simulations and X-ray diffraction/PDF refinements was used successfully to model the local atomic structure in La1 12xBa1+xGaO4 12x/2, thus suggesting that this approach could be positively applied in general to disordered systems

Oxygen transport in nanostructured lanthanum manganites

Methods and models describing oxygen diffusion and desorption in oxides have been developed for slightly defective and well crystallised bulky materials. Does nanostructuring change the mechanism of oxygen mobility? In such a case, models should be properly checked and adapted to take into account new material properties. In order to do so, temperature programmed oxygen desorption and thermogravimetric analysis, either in isothermal or ramp mode, have been used to investigate some nanostructured La1\u2013xAxMnO3 d samples (A = Sr and Ce, 20\u201360 nm particle size) with perovskite-like structure. The experimental data have been elaborated by means of different models to define a set of kinetic parameters able to describe oxygen release properties and oxygen diffusion through the bulk. Different rate-determining steps have been identified, depending on the temperature range and oxygen depletion of the material. In particular, oxygen diffusion was shown to be rate-limiting at low temperature and at low defect concentration, whereas oxygen recombination at the surface seems to be the rate-controlling step at high temperature. However, the oxygen recombination step is characterised by an activation energy much lower than that for diffusion. In the present paper oxygen transport in nanosized materials is quantified by making use of widely diffused experimental techniques and by critically adapting to nanoparticles suitably chosen models developed for bulk materials

Phase Transformations in the CeO2-Sm2O3System : A Multiscale Powder Diffraction Investigation

The structure evolution in the CeO2-Sm2O3system is revisited by combining high resolution synchrotron powder diffraction with pair distribution function (PDF) to inquire about local, mesoscopic, and average structure. The CeO2fluorite structure undergoes two phase transformations by Sm doping, first to a cubic (C-type) and then to a monoclinic (B-type) phase. Whereas the C to B-phase separation occurs completely and on a long-range scale, no miscibility gap is detected between fluorite and C-type phases. The transformation rather occurs by growth of C-type nanodomains embedded in the fluorite matrix, without any long-range phase separation. A side effect of this mechanism is the ordering of the oxygen vacancies, which is detrimental for the application of doped ceria as an electrolyte in fuel cells. The results are discussed in the framework of other Y and Gd dopants, and the relationship between nanostructuring and the above equilibria is also investigated

Relaxor ferroeletric behavior inSr1−xPrxTiO3 : Cooperation between polar and antiferrodistortive instabilities

Chemical doping at the Sr and Ti sites is a feasible way to alter the quantum paraelectric state of SrTiO3 perovskite. Doping with Pr is known to induce relaxor ferroelectricity at room temperature in the Sr1 12xPrxTiO3 solid solution. The relationship between its dielectric properties and structural phase transition has been debated, but no definitive structural argument has been proposed. Here we present a systematic structural study of Sr1 12xPrxTiO3 (0.020 _ x _ 0.150).We establish the structural phase diagram using high-resolution x-ray powder diffraction by finding the antiferrodistortive structural phase transitions for all the compositions studied. By using pair distribution function analysis, we show the mismatch between local and long-range structures in terms of increased local order parameters. Finally, we propose a correlation between the local structural order parameters and the emergence of hard polar modes as found by Raman spectroscopy. Our results are quantitatively consistent with recent theoretical calculations showing that the increase of local tetragonality and local octahedral tilting above a critical value in fact underlie the polar instability. This confirms that structural orders involving both polar and antiferrodistortive characters compete and cooperate at different levels, promoting ferroelectricity in Sr1 12xPrxTiO3

Tuning the Interlayer Distance of Graphene Oxide as a Function of the Oxidation Degree for o-Toluidine Removal

Graphene oxide (GO) with different oxidation degrees is prepared by a modified Hummers' method varying KMnO4 amount from 0.5 to 6.0 g. X-ray powder diffraction (XRPD), micro-Raman, thermogravimetric analysis, X-ray photoeelectron spectroscopy, Boehm titrations, high-resolution transmission electron microscopy, and, finally, positron annihilation lifetime spectroscopy (PALS) are exploited to assess the properties of GO. Results show that increasing oxidant species can tune the interlayer gap between GO sheets up to a maximum value in the case of 4.0 g KMnO4 content. Moreover, these results validate the two-component-based model of GO in which, at low oxidation degree, there are unsplit/isolated graphene planes, instead at higher oxidant amounts, a five-layer sandwiched configuration occurs comprising graphene planes having functional groups decorating the edges (bwGO), hydrated oxidative debris (OD) and "empty" spaces (revealed by PALS as the distance between (bwGO + OD) two-component layers). In addition, by XRPD analysis, the total gap between two sheets is easily computed. In order to correlate these findings to pollutant removal capability, planar o-toluidine adsorption is studied. Since this molecule diffuses in an aqueous environment, the obtained adsorption percentages are compared to the thickness of the hydrated OD grafted onto bwGO. A strict connection between the pollutant removal efficacy and the variation of the hydrated interlayer distance is found

Differential Pair Distribution Function applied to Ce1-xGdxO2-x/2 system

The Pair Distribution Function technique based upon X-ray diffraction data is a powerful tool to unveil disorder on the nanometric scale, which is however element insensi-tive. To overcome this problem, Differential Pair Distribution Functions (DPDF) can be obtained by exploiting the anomalous dispersion of X-rays near the absorption edge of a certain element. In this paper the DPDF method is briefly reviewed and applied to the case of gadolinium doped ceria electrolytes. XRPD data have been collected at the Ce-K edge on the ID31 beamline of the European Synchrotron Radiation Facility (ESRF). The validity of this approach to extract chemical specific information is also briefly discussed

Defect clustering in Ce1-xGdxO2-x/2 using the PDF Analysis

Aim of this work is to unveil the complex positional disorder induced by gadolinium doping and oxygen vacancies formation in Ce1-xGdxO2-x/2 (CGO) electrolytes for solid oxide fuel cells by means of the Pair Distribution Function (PDF) analysis. The whole range of Gd concentration xGd (0 ~10 \uc5. The same models applied at lower r values fails to reproduce the experimental curves. A clear improvement of the fit quality in the 1.5 < r < ~6 \uc5 range was obtained for all the CGO samples applying a biphasic model encompassing both a fluorite CeO2-like and a C-type Gd2O3-like phases. This provides evidence that extended defects at local scale exist in the CGO. Gd-rich and Ce-rich droplets coexist in the sub-nanometric range

Charge ordering transition in GdBaCo2O5: evidence of reentrant behavior

We present a detailed study on the charge ordering (CO) transition in GdBaCo2O5 system by combining high resolution synchrotron powder/single crystal diffraction with electron paramagnetic resonance (EPR) experiments as a function of temperature. We found a second order structural phase transition at TCO=247 K (Pmmm to Pmma) associated with the onset of long range CO. At Tmin = 1.2TCO, the EPR linewidth rapidly broadens providing evidence of spin fluctuations due to magnetic interactions between Gd3+ ions and antiferromagnetic couplings of Co2+/Co3+ sublattices. This likely indicates that, analogously to manganites, the long-range antiferromagnetic order in GdBaCo2O5 sets in at TCO. Pair distribution function (PDF) analysis of diffraction data revealed signatures of structural inhomogeneities at low temperature. By comparing the average and local bond valences, we found that above TCO the local structure is consistent with a fully random occupation of Co2+ and Co3+ in a 1:1 ratio and with a complete charge ordering below TCO. Below T = 100 K the charge localization is partially melted at the local scale, suggesting a reentrant behavior of CO. This result is supported by the weakening of superstructure reflections and the temperature evolution of EPR linewidth that is consistent with paramagnetic (PM) reentrant behavior reported in the GdBaCo2O5.5 parent compound.Comment: 30 pages, 10 figure

Rare earth doped ceria: The complex connection between structure and properties

The need for high efficiency energy production, conversion, storage and transport is serving as a robust guide for the development of new materials. Materials with physical-chemical properties matching specific functions in devices are produced by suitably tuning the crystallographic- defect- and micro-structure of the involved phases. In this review, we discuss the case of Rare Earth doped Ceria. Due to their high oxygen diffusion coefficient at temperatures higher than ~500\ub0C, they are very promising materials for several applications such as electrolytes for Solid Oxide Fuel and Electrolytic Cells (SOFC and SOEC, respectively). Defects are integral part of the conduction process, hence of the final application. As the fluorite structure of ceria is capable of accommodating a high concentration of lattice defects, the characterization and comprehension of such complex and highly defective materials involve expertise spanning from computational chemistry, physical chemistry, catalysis, electrochemistry, microscopy, spectroscopy, and crystallography. Results coming from different experimental and computational techniques will be reviewed, showing that structure determination (at different scale length) plays a pivotal role bridging theoretical calculation and physical properties of these complex materials

Convenient Preparation of Graphene Oxide from Expandable Graphite and Its Characterization by Positron Annihilation Lifetime Spectroscopy

Graphene oxide (GO) is conveniently prepared from expandable graphite using a simplified Hummers\u2019 method. The product is thoroughly characterized by usual techniques (UV-vis, Fourier-transform infrared (FTIR) and Raman spectroscopies, zeta potential, electron microscopy, X-ray diffraction, nitrogen adsorption) to confirm the success of synthesis. Positron annihilation lifetime spectroscopy (PALS) is then used to extract information on the microenvironment in between the layers of graphene oxid