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This work is devoted to evaluating the relationship between the oxygen content and catalytic activity in the CO oxidation process of the 6H-type BaFeO3-δ system. Strong evidence is provided about the improvement of catalytic performance with increasing Fe average oxidation state, thus suggesting the involvement of lattice oxygen in the catalytic process. The compositional and structural changes taking place in both the anionic and cationic sublattices of the catalysts during redox cycles have been determined by temperature-resolved neutron diffraction. The obtained results evidence a structural transition from hexagonal (P63/mmc) to orthorhombic (Cmcm) symmetry. This transition is linked to octahedra distortion when the Fe3+ concentration exceeds 40% (δ values higher than 0.2). The topotactical character of the redox process is maintained in the δ range 0 < δ < 0.4. This suggests that the cationic framework is only subjected to slight structural modifications during the oxygen exchange process occurring during the catalytic cycle.
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The elucidation of the reaction mechanisms involving redox processes in functional transition-metal oxides, which usually start in areas of very few nanometers in size, is yet a challenge to be satisfactorily achieved. Atomically resolved HAADF and EELS have provided both chemical and structural information at the nanoscale, which reveal the preservation of short-range cationic order in areas of 2-3 nm length as the driving force behind the reversibility of the Ca2Mn3O8-Ca2Mn3O5 redox process. Oxygen evolution is accommodated by cationic diffusion along the Ca and Mn layers of the cation-deficient Ca2Mn3O8 delafossite related structure, whereas Mn remains octahedrally coordinated.
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A new perovskite cathode, Sr0.95Ce0.05CoO3-δ, performs well for oxygen-reduction reactions in solid oxide fuel cells (SOFCs). We gain insight into the crystal structure of Sr1-xCexCoO3-δ (x = 0.05, 0.1) and temperature-dependent structural evolution of Sr0.95Ce0.05CoO3-δ by X-ray diffraction, neutron powder diffraction, and scanning transmission electron microscopy experiments. Sr0.9Ce0.1CoO3-δ shows a perfectly cubic structure (a = a0), with a large oxygen deficiency in a single oxygen site; however, Sr0.95Ce0.05CoO3-δ exhibits a tetragonal perovskite superstructure with a double c axis, defined in the P4/mmm space group, that contains two crystallographically different cobalt positions, with distinct oxygen environments. The structural evolution of Sr0.95Ce0.05CoO3-δ at high temperatures was further studied by in situ temperature-dependent NPD experiments. At 1100 K, the oxygen atoms in Sr0.95Ce0.05CoO3-δ show large and highly anisotropic displacement factors, suggesting a significant ionic mobility. The test cell with a La0.8Sr0.2Ga0.83Mg0.17O3-δ-electrolyte-supported (â¼300 µm thickness) configuration yields peak power densities of 0.25 and 0.48 W cm(-2) at temperatures of 1023 and 1073 K, respectively, with pure H2 as the fuel and ambient air as the oxidant. The electrochemical impedance spectra evolution with time of the symmetric cathode fuel cell measured at 1073 K shows that the Sr0.95Ce0.05CoO3-δ cathode possesses superior ORR catalytic activity and long-term stability. Mixed ionic-electronic conduction properties of Sr0.95Ce0.05CoO3-δ account for its good performance as an oxygen-reduction catalyst.
Assuntos
Cério/química , Cobalto/química , Fontes de Energia Elétrica , Estrôncio/química , Cristalografia por Raios X , Eletrodos , Oxirredução , TemperaturaRESUMO
SmFeO3 has attracted considerable attention very recently due to its reported multiferroic properties above room temperature. We have performed powder and single crystal neutron diffraction as well as complementary polarization dependent soft X-ray absorption spectroscopy measurements on floating-zone grown SmFeO3 single crystals in order to determine its magnetic structure. We found a k=0 G-type collinear antiferromagnetic structure that is not compatible with inverse Dzyaloshinskii-Moriya interaction driven ferroelectricity. While the structural data reveal a clear sign for magneto-elastic coupling at the Néel-temperature of â¼675 K, the dielectric measurements remain silent as far as ferroelectricity is concerned.
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A report from the International Union of Crystallography Commission on Magnetic Structures outlining the recommendations for communicating commensurate magnetic structures.
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Double perovskites containing Ir(6+)/Ir(5+) with formula Sr2MIrO6 (M = Ni, Zn) have been synthesized under high oxygen pressure conditions. Their crystal structures have been studied by X-ray and neutron powder diffraction at room temperature (RT) and 2 K. At RT, these oxides crystallize in the monoclinic space group P2(1)/n with unit-cell parameters a ≈ â2a0, b ≈ â2a0, and c ≈ 2a0, and ß ≈ 90°. The thermal evolution of the structure of the Ni-containing compound shows the presence of two phase transition in the 373-673 K interval following the sequence P2(1)/n â I4/m â Fm3m. These materials have also been characterized by magnetic measurements, suggesting the onset of antiferromagnetic interactions at T(N) = 58 and 46 K, for M = Ni, Zn, respectively. X-ray absorption spectroscopy sheds light on the oxidation states of M and Ir ions within these double perovskites.
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We report on measurements, by polarized neutron elastic scattering, of the magnetization distribution induced in a single crystal of URu2Si2 under a magnetic field applied along the tetragonal c axis. A subtle change in this distribution, revealed by maximum entropy analysis of the data, is found when the temperature is decreased to the range of the hidden order. An analysis in terms of U(4+) ionic states reveals that this change is a fingerprint of a freezing of rank 5 multipoles, i.e., dotriacontapoles.
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The temperature-pressure phase diagram for both the crystal and magnetic structures of LaCrO(3) perovskite has been mapped out by in situ neutron-diffraction experiments under pressure. The system offers the opportunity to study the evolution of magnetic order, spin direction, and magnetic moment on crossing the orthorhombic-rhombohedral phase boundary. Moreover, a microscopic model of the superexchange interaction has been developed on the basis of the crystal structure obtained in this work to account for the behavior of T(N) under high pressure.
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The metal-insulator transition occurring in hollandite K2V8O16 has been studied by means of neutron and x-ray diffraction as well as by thermodynamic and electron-spin resonance measurements. The complete analysis of the crystal structure in the distorted phase allows us to identify dimerization as the main distortion element in insulating K2V8O16. At low-temperature, half of the V chains are dimerized perfectly explaining the suppression of magnetic susceptibility due to the formation of spin singlets. The dimerization is accompanied by the segregation of charges into chains.
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The oxides of the SrCo(1-x)Sb(x)O(3-δ) perovskite family have been recently designed, characterized and described as cathode materials for solid-oxide fuel cells with competitive power performance in the temperature range 750-850 °C. They feature a number of interesting properties including a good electronic conductivity, low electrode polarization resistance and adequate thermal expansion; the crystal structure adopts a 3C corner-linked perovskite network with a considerable number of oxygen vacancies. This paper reports on the effects of Sb-doping on the crystal structure features, the Co oxidation state and magnetic properties related to the presence of spin-state transitions in the Co cations. A phase transition was observed from the tetragonal P4/mmm space group for x≤ 0.15 to the cubic Pm Ì 3m space group in the x = 0.2 composition from neutron powder diffraction data. For the tetragonal phases the oxygen vacancies were found to be ordered and localized in the axial O2 and equatorial O3 atoms surrounding the Co2 positions. A noticeable distortion of CoO(6) octahedra is observed for x = 0.05 and 0.1, exhibiting a charge-ordering with a mixed oxidation state of Co(3+/4+) at Co1 sites and Co(3+) at Co2 positions: the Jahn-Teller Co(3+) in an intermediate-spin configuration is responsible for the octahedral distortion. Increasing Sb contents promotes a higher average oxidation state of cobalt, from a valence of 3.2+ for x = 0.05 to 3.4+ for x = 0.2, inducing a decrease of the oxygen vacancies and favouring a random distribution over a Pm Ì 3m cubic symmetry. All the samples present an antiferromagnetic behaviour with a G-type (k = 0) magnetic structure. The increase of the Sb content induces the weakening of the crystal field (Δ(cf)) in the octahedral environment promoting the Co spin-transition from the intermediate-spin to the high-spin configuration, as evidenced by the decrease of the octahedral distortion, increment of the unit-cell volume and enhancement of the ordered magnetic moment.
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The elusive crystal structure of the so-called 'antimonic acid' has been investigated by means of robust and state-of-the-art techniques. The synergic results of solid-state magic-angle spinning nuclear magnetic resonance spectroscopy and a combined Rietveld refinement from synchrotron X-ray and neutron powder diffraction data reveal that this compound contains two types of protons, in a pyrochlore-type structure of stoichiometric formula (H3O)1.20(7)H0.77(9)Sb2O6. Some protons belong to heavily delocalized H3O+ subunits, while some H+ are directly bonded to the oxygen atoms of the covalent framework of the pyrochlore structure, with O-H distances close to 1 Å. A proton diffusion mechanism is proposed relying on percolation pathways determined by bond-valence energy landscape analysis. X-ray absorption spectroscopy results corroborate the structural data around Sb5+ ions at short-range order. Thermogravimetric analysis and differential scanning calorimetry endorsed the conclusions on the water content within antimonic acid. Additional 0.7 water molecules per formula were assessed as moisture water by thermal analysis.
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Scientific interest in iron-oxides and in particular magnetite has been renewed due to the broad scope of their fascinating properties, which are finding applications in electronics and biomedicine. Specifically, iron oxide nanoparticles (IONPs) are gathering attraction in biomedicine. Their cores are usually constituted by a mixture of maghemite and magnetite phases. In view of this, to fine-tune the properties of an ensemble of IONPs towards their applications, it is essential to enhance mass fabrication processes towards the production of monodisperse IONPs with controlled size, shape, and stoichiometry. We exploit the vacancy sensitivity of the Verwey transition to detect the presence of magnetite. Here we provide direct evidence for the Verwey transition in an ensemble of IONPs through neutron diffraction. This transition is observed as a variation in the Fe magnetic moment at octahedral sites and, in turn, gives rise to a change of the net magnetic moment. Finally, we show this variation as the microscopic ingredient driving the characteristic kink that hallmarks the Verwey transition in thermal variation of magnetization.
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The knowledge of the oxidation state of the transition metal cations in Sr(2)FeMO(6) (M = W, Mo, Re and Sb) double perovskites is of paramount importance to understand their appealing magnetoresistive or magnetic properties. We present a systematic investigation of the valences of Fe, W, Mo, Re and Sb cations in these perovskites using three different and complementary techniques of analysis. We have used a diffraction method, neutron powder diffraction (NPD), coupled with the bond-valence model; and two spectroscopy methods, X-ray photoemission spectroscopy (XPS) and X-ray absorption spectroscopy (XAS). These two techniques are also complementary since XPS analyses the surface of the samples whereas XAS probes the bulk material. The analysis of the Fe K-edge spectra of the four samples shows a clear shift of the Fe K-edge as the valence of iron increases in the sequence M = W, Mo, Re and Sb. In addition, XANES pre-edge structures unveil a progressive reduction in the occupancy level of the Fe-3d band as the oxidation state of iron increases along the sequence M = W, Mo, Re and Sb. Finally, XANES computations have determined the electronic structures of Sr(2)FeWO(6), Sr(2)FeMoO(6), Sr(2)FeReO(6) and Sr(2)FeSbO(6).
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New polycrystalline SrMo1-xMxO4-δ (M = Fe and Cr) scheelite oxides have been prepared by topotactical oxidation, by annealing in air at 500 °C, from precursor perovskites with the stoichiometry SrMo1-xMxO3-δ (M = Fe and Cr). An excellent reversibility between the oxidized Sr(Mo,M)O4-δ scheelite and the reduced Sr(Mo,M)O3-δ perovskite phase accounts for the excellent behavior of the latter as anode material in solid-oxide fuel cells. A characterization by X-ray powder diffraction (XRD) and neutron powder diffraction (NPD) has been carried out to determine the crystal structure features. The scheelite oxides are tetragonal, space group I41/a (No. 88). The Rietveld-refinement from NPD data at room temperature shows evidence of oxygen vacancies in the structure, due to the introduction of Fe3+/Cr4+ cations in the tetrahedrally-coordinated B sublattice, where Mo is hexavalent. A thermal analysis of the reduced perovskite (SrMo1-xMxO3-δ) in oxidizing conditions confirms the oxygen stoichiometry obtained by NPD data; the stability range of the doped oxides, below 400-450 °C, is lower than that for the parent SrMoO3 oxide. The presence of a Mo4+/Mo5+ mixed valence in the reduced SrMo1-xMxO3-δ perovskite oxides confers greater instability against oxidation compared with the parent oxide. Finally, an XPS study confirms the surface oxidation states of Mo, Fe, and Cr in the oxidized samples SrMo0.9Fe0.1O4-δ and SrMo0.8Cr0.2O4-δ.
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The crystal structure of the Sb6O13 oxide, exhibiting a defect pyrochlore crystal structure with atomic vacancies, has been studied using a complete set of state-of-the-art techniques. The degree of antimony disproportionation in Sb3+ and Sb5+ valence states has been directly determined around 36% and 64%, respectively, using X-ray absorption near edge structure (XANES). These findings are in excellent agreement with our Rietveld analysis of synchrotron X-ray (SXRD) and neutron powder diffraction (NPD) results. Moreover, the highly distorted Sb3+ coordination due to its lone electron pair has been critically revisited. The bonding distances and coordination of Sb3+ and Sb5+ species closely agree with an extensive dynamic and crystallographic determination using the Extended X-ray Absorption Fine Structure (EXAFS) technique. Most importantly, the specific local disorder of the two distinctive Sb ions has been crosschecked monitoring their unusual Debye-Waller factors.
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Developing efficient and low-cost electrocatalysts for the oxygen evolution reaction (OER) is of paramount importance to many chemical and energy transformation technologies. The diversity and flexibility of metal oxides offer numerous degrees of freedom for enhancing catalytic activity by tailoring their physicochemical properties, but the active site of current metal oxides for OER is still limited to either metal ions or lattice oxygen. Here, a new complex oxide with unique hexagonal structure consisting of one honeycomb-like network, Ba4 Sr4 (Co0.8 Fe0.2 )4 O15 (hex-BSCF), is reported, demonstrating ultrahigh OER activity because both the tetrahedral Co ions and the octahedral oxygen ions on the surface are active, as confirmed by combined X-ray absorption spectroscopy analysis and theoretical calculations. The bulk hex-BSCF material synthesized by the facile and scalable sol-gel method achieves 10 mA cm-2 at a low overpotential of only 340 mV (and small Tafel slope of 47 mV dec-1 ) in 0.1 m KOH, surpassing most metal oxides ever reported for OER, while maintaining excellent durability. This study opens up a new avenue to dramatically enhancing catalytic activity of metal oxides for other applications through rational design of structures with multiple active sites.
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We report on the magnetic structure of CdMn7O12 determined by powder neutron diffraction. We were able to measure the magnetic structure of this Cd containing and highly neutron absorbing material by optimizing the sample geometry and by blending the CdMn7O12 with Aluminum powder. Below its Néel temperature TN1 all magnetic reflections can be indexed by a single commensurate propagation vector k = (0, 0, 1). This is different to the case of CaMn7O12 where the propagation vector is incommensurate and where an in-plane helical magnetic structure has been found. We observe a commensurate non-collinear magnetic structure in CdMn7O12 with in-plane aligned magnetic moments resembling the ones in CaMn7O12. However, the commensurate propagation vector prevents the appearance of a helical magnetic structure in CdMn7O12. Finally, we also observe a third structural phase transition below ~60 K that can be attributed to phase separation.
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Sb-doped Bi2Te3 is known since the 1950s as the best thermoelectric material for near-room temperature operation. Improvements in material performance are expected from nanostructuring procedures. We present a straightforward and fast method to synthesize already nanostructured pellets that show an enhanced ZT due to a remarkably low thermal conductivity and unusually high Seebeck coefficient for a nominal composition optimized for arc-melting: Bi0.35Sb1.65Te3. We provide a detailed structural analysis of the Bi2-xSbxTe3 series (0 ≤ x ≤ 2) based on neutron powder diffraction as a function of composition and temperature that reveals the important role played by atomic vibrations. Arc-melting produces layered platelets with less than 50 nm-thick sheets. The low thermal conductivity is attributed to the phonon scattering at the grain boundaries of the nanosheets. This is a fast and cost-effective production method of highly efficient thermoelectric materials.
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Thermoelectric materials may contribute in the near future as new alternative sources of sustainable energy. Unprecedented thermoelectric properties in p-type SnSe single crystals have been recently reported, accompanied by extremely low thermal conductivity in polycrystalline samples. In order to enhance thermoelectric efficiency through proper tuning of this material we report a full structural characterization and evaluation of the thermoelectric properties of novel Ge-doped SnSe prepared by a straightforward arc-melting method, which yields nanostructured polycrystalline samples. Ge does not dope the system in the sense of donating carriers, yet the electrical properties show a semiconductor behavior with resistivity values higher than that of the parent compound, as a consequence of nanostructuration, whereas the Seebeck coefficient is higher and thermal conductivity lower, favorable to a better ZT figure of merit.
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In the course of an investigation to prepare the hypothetic new double perovskite La(3)Co(2)VO(9) with Co(2+) and V(5+) in octahedral sites, we obtained the new simple perovskite LaCo(0.71(1))V(0.29(1))O(2.97(3)) as the main phase. The pure compound was then synthesized by the citrate decomposition method. The crystal structure was studied by X-ray (PXRD) and powder neutron diffraction (PND). Physical properties were characterized by X-ray absorption spectroscopy (XAS), X-ray emission spectroscopy (XES) and thermogravimetric analysis (TGA). Rietveld refinements were performed in the orthorhombic space group Pnma (#62). Refined cell parameters were a = 5.4762(2) Å, b = 7.7609(2) Å and c = 5.5122(1) Å. Magnetization measurements showed that this perovskite is an antiferromagnet with a Neel temperature of 15 K. At high T the magnetization follows the Curie-Weiss law corrected by temperature independent paramagnetism (TIP) showing an effective magnetic moment of 3.03µ(B) well described by the contribution of Co(2+) (HS), Co(3+) (IS), V(3+) and V(4+) ions. The crystallographic formula was refined by PND and oxidation state distribution was determined by the combination of PND, XAS, TGA and magnetic measurements.