A XAFS investigation of amorphous-to-crystalline and fluorite-to-pyrochlore phase transitions in Ln2M2O7 (Ln= Gd, Tb, Dy; M= Ti, Zr)

Amorphous-to-crystalline and fluorite-to-pyrochlore phase transitions in complex oxides Ln2M2O7 (Ln = Gd, Tb, Dy; M = Ti, Zr) prepared by sol-gel and coprecipitation methods were studied using x-ray absorption spectroscopy in combination with x-ray diffraction and Raman spectroscopy. The Ln titanates crystallize directly from the amorphous state to the pyrochlore structure, while the Ln zirconates form the intermediate fluorite phase first. We have found that both XANES and EXAFS data reflect the considerable difference between the crystallization processes of Ln titanates and zirconates. In particular the evolution of the K–Ti pre-edge features is a good indicator of the phase transition from amorphous to crystalline state. The splitting of the first Ln-O shell in the FT modulus of L3-Ln edge EXAFS spectra in Ln titanates can be regarded as a fingerprint of the ordered pyrochlore structure formation which is accompanied also by specific changes in the main features of the XANES spectra. For the Ln zirconates these features are less pronounced

Specific features of the crystal and local structures of compounds formed in the Dy2O3–HfO2Dy_{2}O_{3}–HfO_{2} system

The crystal and local structures of compounds formed in the Dy$_2$O$_3$–HfO$_2$ system (at molar ratios from 1: 3 to 3: 1) in the course of isothermal annealing of X-ray amorphous mixed hydroxides at temperatures up to 1600°C have been studied. At the molar ratio Dy$_2$O$_3$: HfO$_2$ from 1: 3 to 1: 1, crystallization leads to formation of single-phase defect fluorite solid solutions nDy$_2$O$_3$ ∙ mHfO$_2$ with clearly pronounced nonequivalence of parameters of local environment of Dy$^{3+}$ and Hf$^{4+}$ cations. It has been found that Dy$_2$H$_2$O$_7$ (Dy$_2$O$_3$: HfO$_2$ = 1: 2) samples have a tendency to pyrochlore-type ordering in both the cationic and anionic sublattices

Fluorite-pyrochlore phase transition in nanostructured Ln2Hf2O7\mathrm{Ln_{2}Hf_{2}O_{7}} (Ln = La-Lu)

Complex oxides of the Ln$_{2}$Hf$_{2}$O$_{7}$ (Ln = lanthanide) series undergo a fluorite to pyrochlore phase transformation. We have studied the whole process of the crystal and local atomic structure realignment during the crystallization and the phase transition in the series of Ln$_{2}$Hf$_{2}$O$_{7}$ (Ln = La-Lu) samples synthesized by the coprecipitation method with the subsequent annealing of mixed hydroxides (precursors). The study employed a combination of x-ray diffraction (normal and anomalous), x-ray absorption spectroscopy, analysis of atomic pair distribution function and Raman spectroscopy. The starting and ending temperatures of the fluorite-pyrochlore phase transition for Ln$_{2}$Hf$_{2}$O$_{7}$ compounds have been determined along the lanthanide series La-Dy. The scheme summarizing structure types (amorphous, fluorite and pyrochlore) for the whole Ln2Hf2O7 (Ln = La-Lu) series as a function of the Ln cation radius (or the r$_{Ln3+}/r_{Hf4+} ratio) and the annealing temperature has been refined

Formation and evolution of crystal and local structures in nanostructured Ln2Ti2O7 (Ln = Gd–Dy)

The lanthanide titanates Ln2Ti2O7 (Ln = lanthanide) demonstrate a very broad range of structural, chemical and physical properties. We have studied the whole process of the crystallization and local atomic structure rearrangement in Ln2Ti2O7 (Ln = Gd, Tb, Dy) samples synthesized by combination of sol-gel and coprecipitation methods with the subsequent calcination of Ln-Ti precursors. X-ray absorption spectroscopy (XAFS), X-ray powder diffraction, infrared spectroscopy, Raman spectroscopy, scanning electron microscopy with energy dispersive X-ray spectroscopy and simultaneous thermal analysis were used for the complex analysis of the structural properties. It was shown that crystallization of amorphous precursors directly resulted in the formation of nanocrystalline powders with the pyrochlore structure which is formed in process of ordering of both cationic and anionic sublattices. We have demonstrated that both XAFS and Raman spectroscopy ensure the particularly sensitive markers of changes in local electronic and crystal structure of Ln2Ti2O7 depending on the type of Ln element and the preparation procedure. It was established that splitting of the first Ln-O shell in the FT modulus of L3-Ln EXAFS spectra appears to be the reliable indicator of the ordered pyrochlore structure formation, while the changes in the pre-edge region of the K-Ti XANES spectra reflect the process of the Ln2Ti2O7 electronic structure formation

Magnetization of crystalline and amorphous phases of R2Ti2O7 and R2Zr2O7 (R= Gd, Dy, Tb)

We present the study of frustrated magnets R2M2O7, where R = Gd, Dy, Tb and M = Ti, Zr. Magnetic susceptibility χ and low-temperature magnetization of perfectly ordered pyrochlores R2Ti2O7, partially disordered fluorites R2Zr2O7, and their completely disordered amorphous phases were measured and analyzed. We have found that structural disorder weakens the exchange interaction of the rare-earth ions. Magnetic moments of dysprosium and terbium, obtained from nearly saturated magnetization, are slightly affected by the disorder while the gadolinium moment is completely independent of it. The local structure of the compounds, including oxygen environment of the rare-earth ions, is discussed in terms of the influence of the crystal electric field on the magnetic properties of R2M2O7

Features of the Phase Preferences, Long- and Short-Range Order in <i>Ln</i>₂(WO₄)₃ (<i>Ln</i> = Gd, Dy, Ho, Yb) with Their Relation to Hydration Behavior

The effect of synthesis conditions on the features of the long- and short-range order of Ln2(WO4)3 (Ln = Gd, Dy, Ho, Yb) powders synthesized via coprecipitation of salts has been studied by a complex of physico-chemical techniques including synchrotron X-ray powder diffraction, X-ray absorption spectroscopy, Raman and infrared spectroscopy, and simultaneous thermal analysis. It was found that crystallization of amorphous precursors begins at 600 °C/3 h and leads to the formation of the monoclinic structure with sp. gr. C12/c1(15) for Ln2(WO4)3 (Ln = Gd, Dy) and with sp. gr. P121/a1(14) for Ln = Yb, whereas crystallization of Ho precursor requires even higher temperature. After annealing at 1000 °C, the P121/a1(14) phase becomes the dominant phase component for all heavy lanthanoid types except for Ln = Gd. It was shown that the Ln (Ln = Dy, Ho, and Yb) tungstates with the P121/a1(14) monoclinic structure correspond to trihydrates Ln2(WO4)3·3H2O formed due to a rapid spontaneous hydration under ambient conditions. It was concluded that the proneness to hydration is due to a specific structure of the P121/a1(14) phase with large voids available to water molecules. Modifications in the local structure of Ln-O coordination shell accompanying the structure type change and hydration are monitored using EXAFS spectroscopy

Direct evidence of real-space pairing in BaBiO3

The parent compound BaBiO3 of bismuthate high-temperature superconductors (HTSCs) BaBi(Pb)O3 and Ba(K)BiO3 with perovskitelike structure exhibits unusual electronic and structural properties, which can be satisfactorily explained if we assume that all charge carriers are in the paired state. However, the prior experiments and the first-principle calculations only indirectly indicate the existence of paired charge carriers in BaBiO3. In this work, we report the direct evidence of initially paired electrons and holes in the upper antibonding Bi 6s-O 2p sigma* orbital of the neighboring octahedral complexes in the ground state of BaBiO3 using the time-resolved x-ray absorption spectroscopy (XAS) to monitor the electron dynamics after the femtosecond resonant 633 nm laser excitation. We observe strong changes in the oxygen K-edge XAS preedge region, defined by the Bi 6s-O 2p sigma* orbitals. We interpret them as a fast (&lt;= 0.3 ps) breaking of charge carrier pairs and slower (0.3-0.8 ps) lattice rearrangement from the distorted monoclinic structure into the new metastable state with a cubic lattice, which persists at least up to 60 ps after the excitation. Analysis of the intermediate state at the fast excitation shows that the bond disproportionation and monoclinic distortion of BaBiO3 structure are energetically favorable due to the charge carrier pairing. Thus the compound BaBiO3 forms a new quantum state that we define as a local pair density wave. Taking into account a large number of similarities between bismuthate and cuprate high-temperature superconductors, we believe that our work will give a new impetus to understanding the nature of superconductivity in perovskite HTSCs

Influence of Synthesis Conditions on the Crystal, Local Atomic, Electronic Structure, and Catalytic Properties of (Pr_1−<i>x</i>Yb_<i>x</i>)₂Zr₂O₇ (0 ≤ <i>x</i> ≤ 1) Powders

The influence of Yb3+ cations substitution for Pr3+ on the structure and catalytic activity of (Pr1−xYbx)2Zr2O7 powders synthesized via coprecipitation followed by calcination is studied using a combination of long- (s-XRD), medium- (Raman, FT-IR, and SEM-EDS) and short-range (XAFS) sensitive methods, as well as adsorption and catalytic techniques. It is established that chemical composition and calcination temperature are the two major factors that govern the phase composition, crystallographic, and local-structure parameters of these polycrystalline materials. The crystallographic and local-structure parameters of (Pr1−xYbx)2Zr2O7 samples prepared at 1400 °C/3 h demonstrate a tight correlation with their catalytic activity towards propane cracking. The progressive replacement of Pr3+ with Yb3+ cations gives rise to an increase in the catalytic activity. A mechanism of the catalytic cracking of propane is proposed, which considers the geometrical match between the metal–oxygen (Pr–O, Yb–O, and Zr–O) bond lengths within the active sites and the size of adsorbed propane molecule to be the decisive factor governing the reaction route