Synergic Effect of Metal and Fluorine Doping on the Structural and Electrical Properties of La5.4MoO11.1-Based Materials.

Cationic and anionic frameworks of La5.4MoO11.1 proton conductors have been modified by means of metal (Ti4+, Zr4+, and Nb5+) and fluorine (F-) doping. This synergic effect leads to the stabilization of high-symmetry and single-phase polymorphs. The materials have been fully characterized by structural techniques, such as X-ray and neutron powder diffraction and transmission electron microscopy. The fluorine content was determined by ion chromatography. Impedance spectroscopy analysis under different atmospheres (dry and wet N2 and O2 and wet 5% H2-Ar) showed an improvement in the electronic conductivity under reducing conditions, making these materials potential candidates for hydrogen separation membranes.

Relationship between the Structure and Transport Properties in the Ce1-xLaxO2-x/2 System.

La-doped CeO2 materials have been widely investigated for potential applications in different high-temperature electrochemical devices, such as fuel cells and ceramic membranes for hydrogen production. However, the crystal structure is still controversial, and different models based on fluorite, pyrochlore, and/or type-C structures have been considered, depending on the lanthanum content and synthesis method used. In this work, an exhaustive structural analysis of the Ce1-xLaxO2-x/2 system (0.2 < x ≤ 0.7) is performed with different techniques. The average crystal structure, studied by conventional X-ray diffraction, could be considered to be a disordered fluorite; however, the local structure, examined by electron diffraction and Raman spectroscopy, reveals a biphasic mixture of fluorite and C-type phases. The thermal and electrical properties demonstrate that the materials with x ≥ 0.4 are oxide ion proton conductors in an oxidizing atmosphere and mixed ionic electronic conductors in a reducing atmosphere. The water uptake and proton conductivity increase gradually with the increase in La content, suggesting that the formation of the C-type phase is responsible for the proton conduction in these materials.

Metal-Doping of La5.4MoO11.1 Proton Conductors: Impact on the Structure and Electrical Properties.

La5.4MoO11.1 proton conductors with different metal doping (Ca2+, Sr2+, Ba2+, Ti4+, Zr4+, and Nb5+) have been prepared and structurally and electrically characterized. Different polymorphs are stabilized depending on the doping and cooling rate used during the synthesis process. The most interesting results are obtained for Nb-doping, La5.4Mo1- xNb xO11.1- x/2, where single compounds are obtained in the compositional range 0 ≤ x ≤ 0.2. These materials are fully characterized by structural techniques such as X-ray and neutron powder diffraction and transmission electron microscopy, which independently confirm the changes of polymorphism. Scanning electron microscopy and impedance spectroscopy measurements in dry/wet gases (N2, O2, and 5% H2-Ar) showed an enhancement of the sinterability and electrical properties of the materials after Nb-doping. Conductivity measurements under very reducing conditions revealed that these materials are mixed ionic-electronic conductors, making them potential candidates for hydrogen separation membranes.

Influence of Proton Conducting Cations on the Structure and Properties of 2D Anilate-Based Magnets.

The syntheses, structures, magnetic, and proton conductivity properties of a family of bimetallic anilate-based compounds with inserted alkylammonium cations are presented. The structures of (Me2NH2)[MnIICrIII(Br2An)3]·2H2O (1), (Et2NH2)[MnIICrIII(Br2An)3] (2), (Et3NH)[MnIICrIII(Cl2An)3] (3), and [(Et)(i-Pr)2NH][MnIICrIII(Br2An)3]·(CHCl3)0.5·(H2O) (4) contain a 2D anionic network formed by Mn(II) and Cr(III) ions linked through anilate ligands. In 1, 2, and 3, the hexagonal holes of this network are occupied by Me2NH2+, Et2NH2+, or Et3NH+ cations. Interestingly, the small increase of size of the templating cation in 4 ([(Et)(i-Pr)2NH]+ in the place of Me2NH2+, Et2NH2+ or Et3NH+), gives rise to a different structure with half of the cations placed within the layers and the other one in the space between the layers. This leads to bilayers with an interlayer separation similar to those of 1, 2, and 3 separated by larger interbilayer distances. Compounds 1, 2, and 3 show a ferrimagnetic ordering with a Tc of 8.0 K (1), 8.9 K (2), and 8.0 K (3). In 4, the presence of different interlayer distances leads to a metamagnetic behavior when the sample is measured in contact with the mother liquor. The behavior changes in the dry sample, which shows a ferrimagnetic ordering as that of 1, 2, and 3 due to collapse of the structure as confirmed by powder X-ray diffraction. Interestingly, the metamagnetic behavior is recovered after reimmersing the crystals in the mother liquor proving the reversibility of the process. All solids are Grotthuss-type proton conductors with conductivity values ranging between 2.3 × 10-6 S·cm-1 for 3 and 2.4 × 10-5 S·cm-1 for 1 measured at 70 °C and 95% relative humidity and activation energies of ∼0.2 eV.

Luminescent and Proton Conducting Lanthanide Coordination Networks Based On a Zwitterionic Tripodal Triphosphonate.

The synthesis, structural characterization, luminescence properties, and proton conduction performance of a new family of isostructural cationic 2D layered compounds are reported. These have the general formula [Ln(H4NMP)(H2O)2]Cl·2H2O [Ln = La(3+), Pr(3+), Sm(3+), Eu(3+), Gd(3+), Tb(3+), Dy(3+), Ho(3+), H6NMP = nitrilotris(methylphosphonic acid)], and contain Cl(-) as the counterion. In the case of Ce(3+), a 1D derivative, [Ce2(H3NMP)2(H2O)4]·4.5H2O, isostructural with the known lanthanum compound has been isolated by simply crystallization at room temperature. The octa-coordinated environment of Ln(3+) in 2D compounds is composed by six oxygen atoms from three different ligands and two oxygens from each bound water. Two of the three phosphonate groups act as both chelating and bridging linkers, while the third phosphonate group acts solely as a bridging moiety. The materials are stable at low relative humidity at less at 170 °C. However, at high relative humidity transform to other chloride-free phases, including the 1D structure. The proton conductivity of the 1D materials varies in a wide range, the highest values corresponding to the La derivative (σ ≈ 2 × 10(-3) S·cm(-1) at RH 95% and 80 °C). A lower proton conductivity, 3 × 10(-4) S·cm(-1), was measured for [Gd(H4NMP)(H2O)2]Cl·2H2O at 80 °C, which remains stable under the work conditions used. Absorption and luminescence spectra were recorded for selected [Ln(H4NMP)(H2O)2]Cl·2H2O compounds. In all of them, the observed transitions are attributed solely to f-f transitions of the lanthanide ions present, as the H4NMP(2-) organic group has no measurable absorption or luminescence properties.

Guest molecule-responsive functional calcium phosphonate frameworks for tuned proton conductivity.

We report the synthesis, structural characterization, and functionality (framework interconversions together with proton conductivity) of an open-framework hybrid that combines Ca(2+) ions and the rigid polyfunctional ligand 5-(dihydroxyphosphoryl)isophthalic acid (PiPhtA). Ca2[(HO3PC6H3COOH)2]2[(HO3PC6H3(COO)2H)(H2O)2]·5H2O (Ca-PiPhtA-I) is obtained by slow crystallization at ambient conditions from acidic (pH ≈ 3) aqueous solutions. It possesses a high water content (both Ca coordinated and in the lattice), and importantly, it exhibits water-filled 1D channels. At 75 °C, Ca-PiPhtA-I is partially dehydrated and exhibits a crystalline diffraction pattern that can be indexed in a monoclinic cell with parameters close to the pristine phase. Rietveld refinement was carried out for the sample heated at 75 °C, Ca-PiPhtA-II, using synchrotron powder X-ray diffraction data, which revealed the molecular formula Ca2[(HO3PC6H3COOH)2]2[(HO3PC6H3(COO)2H)(H2O)2]. All connectivity modes of the "parent" Ca-PiPhtA-I framework are retained in Ca-PiPhtA-II. Upon Ca-PiPhtA-I exposure to ammonia vapors (28% aqueous NH3) a new derivative is obtained (Ca-PiPhtA-NH3) containing 7 NH3 and 16 H2O molecules according to elemental and thermal analyses. Ca-PiPhtA-NH3 exhibits a complex X-ray diffraction pattern with peaks at 15.3 and 13.0 Å that suggest partial breaking and transformation of the parent pillared structure. Although detailed structural identification of Ca-PiPhtA-NH3 was not possible, due in part to nonequilibrium adsorption conditions and the lack of crystallinity, FT-IR spectra and DTA-TG analysis indicate profound structural changes compared to the pristine Ca-PiPhtA-I. At 98% RH and T = 24 °C, proton conductivity, σ, for Ca-PiPhtA-I is 5.7 × 10(-4) S·cm(-1). It increases to 1.3 × 10(-3) S·cm(-1) upon activation by preheating the sample at 40 °C for 2 h followed by water equilibration at room temperature under controlled conditions. Ca-PiPhtA-NH3 exhibits the highest proton conductivity, 6.6 × 10(-3) S·cm(-1), measured at 98% RH and T = 24 °C. Activation energies (Ea) for proton transfer in the above-mentioned frameworks range between 0.23 and 0.4 eV, typical of a Grothuss mechanism of proton conduction. These results underline the importance of internal H-bonding networks that, in turn, determine conductivity properties of hybrid materials. It is highlighted that new proton transfer pathways may be created by means of cavity "derivatization" with selected guest molecules resulting in improved proton conductivity.

Enhancing the Electrochemical Performance in Symmetrical Solid Oxide Cells through Nanoengineered Redox-Stable Electrodes with Exsolved Nanoparticles.

Symmetrical solid oxide cells (SSOCs) have recently gained significant attention for their potential in energy conversion due to their simplified cell configuration, cost-effectiveness, and excellent reversibility. However, previous research efforts have mainly focused on improving the electrode performance of perovskite-type electrodes through different doping strategies, neglecting microstructural optimization. This work presents novel approaches for the nanostructural tailoring of (La0.8Sr0.2)0.95Fe1-xTixO3-δ (LSFTx, x = 0.2 and 0.4) electrodes using a single-step spray-pyrolysis deposition process. By incorporating these electrodes into a Ce0.9Gd0.1O1.95 (CGO) porous backbone or employing a nanocomposite architecture with nanoscale particle size, we achieved significant improvements in the polarization resistance (Rp) compared with traditional screen-printed electrodes. To further boost the fuel oxidation performance, a Ni-doping strategy, coupled with meticulous microstructural optimization, was implemented. The exsolution of Ni nanoparticles under reducing conditions resulted in remarkable Rp values as low as 0.34 and 0.11 Ω cm2 in air and wet H2 at 700 °C, respectively. Moreover, an electrolyte-supported cell with symmetrical electrodes demonstrated a stable maximum power density of 617 mW cm-2 at 800 °C. These findings highlight the importance of combining electrode composition optimization with advanced morphology control in the design of highly efficient and durable SSOCs.

Influence of Rare-Earth Doping Content and Type on Phase Transformation and Transport Properties in Highly Doped CeO2.

Rare-earth doped CeO2 materials find extensive application in high-temperature energy conversion devices such as solid oxide fuel cells and electrolyzers. However, understanding the complex relationship between structural and electrical properties, particularly concerning rare-earth ionic size and content, remains a subject of ongoing debate, with conflicting published results. In this study, we have conducted comprehensive long-range and local order structural characterization of Ce1-xLnxO2-x/2 samples (x ≤ 0.6; Ln = La, Nd, Sm, Gd, and Yb) using X-ray and neutron powder diffraction, Raman spectroscopy, and electron diffraction. The increase in the rare-earth dopant content leads to a progressive phase transformation from a disordered fluorite structure to a C-type ordered superstructure, accompanied by reduced ionic conductivity. Samples with low dopant content (x = 0.2) exhibit higher ionic conductivity in Gd3+ and Sm3+ series due to lower lattice cell distortion. Conversely, highly doped samples (x = 0.6) exhibit superior conductivity for larger rare-earth dopant cations. Thermogravimetric analysis confirms increased water uptake and proton conductivity with increasing dopant concentration, while the electronic conductivity remains relatively unaffected, resulting in reduced ionic transport numbers. These findings offer insights into the relationship between transport properties and defect-induced local distortions in rare-earth doped CeO2, suggesting the potential for developing new functional materials with mixed ionic oxide, proton, and electronic conductivity for high-temperature energy systems.

Structural variability in multifunctional metal xylenediaminetetraphosphonate hybrids.

Two new families of divalent metal hybrid derivatives from the aromatic tetraphosphonic acids 1,4- and 1,3-bis(aminomethyl)benzene-N,N'-bis(methylenephosphonic acid), (H2O3PCH2)2-N-CH2C6H4CH2-N(CH2PO3H2)2 (designated herein as p-H8L and m-H8L) have been synthesized by crystallization at room temperature and hydrothermal conditions. The crystal structures of M[(HO3PCH2)2N(H)CH2C6H4CH2N(H)(CH2PO3H)2(H2O)2]·2H2O (M = Mg, Co, and Zn), M-(p-H6L), and M[(HO3PCH2)2N(H)CH2C6H4CH2N(H)(CH2PO3H)2]·nH2O (M = Ca, Mg, Co, and Zn and n = 1-1.5), M-(m-H6L), were solved ab initio by synchrotron powder diffraction data using the direct methods and subsequently refined using the Rietveld method. The crystal structure of the isostructural M-(p-H6L) is constituted by organic-inorganic monodimensional chains where the phosphonate moiety acts as a bidentate chelating ligand bridging two metal octahedra. M-(m-H6L) compounds exhibit a 3D pillared open-framework with small 1D channels filled with water molecules. These channels are formed by the pillaring action of the organic ligand connecting adjacent layers through the phosphonate oxygens. Thermogravimetric and X-ray thermodiffraction analyses of M-(p-H6L) showed that the integrity of their crystalline structures is maintained up to 470 K, without significant reduction of water content, while thermal decomposition takes place above 580 K. The utility of M-(p-H6L) (M = Mg and Zn) hybrid materials in corrosion protection was investigated in acidic aqueous solutions. In addition, the impedance data indicate both families of compounds display similar proton conductivities (σ ∼ 9.4 × 10(-5) S·cm(-1), at 98% RH and 297 K), although different proton transfer mechanisms are involved.

High proton conductivity in a flexible, cross-linked, ultramicroporous magnesium tetraphosphonate hybrid framework.

Multifunctional materials, especially those combining two or more properties of interest, are attracting immense attention due to their potential applications. MOFs, metal organic frameworks, can be regarded as multifunctional materials if they show another useful property in addition to the adsorption behavior. Here, we report a new multifunctional light hybrid, MgH(6)ODTMP·2H(2)O(DMF)(0.5) (1), which has been synthesized using the tetraphosphonic acid H(8)ODTMP, octamethylenediamine-N,N,N',N'-tetrakis(methylenephosphonic acid), by high-throughput methodology. Its crystal structure, solved by Patterson-function direct methods from synchrotron powder X-ray diffraction, was characterized by a 3D pillared open framework containing cross-linked 1D channels filled with water and DMF. Upon H(2)O and DMF removal and subsequent rehydration, MgH(6)ODTMP·2H(2)O (2) and MgH(6)ODTMP·6H(2)O (3) can be formed. These processes take place through crystalline-quasi-amorphous-crystalline transformations, during which the integrity of the framework is maintained. A water adsorption study, at constant temperature, showed that this magnesium tetraphosphonate hybrid reversibly equilibrates its lattice water content as a function of the water partial pressure. Combination of the structural study and gas adsorption characterization (N(2), CO(2), and CH(4)) indicates an ultramicroporous framework. High-pressure CO(2) adsorption data are also reported. Finally, impedance data indicates that 3 has high proton conductivity σ = 1.6 × 10(-3) S cm(-1) at T = 292 K at ~100% relative humidity with an activation energy of 0.31 eV.

LaCrO3-CeO2-Based Nanocomposite Electrodes for Efficient Symmetrical Solid Oxide Fuel Cells.

La0.98Cr0.75Mn0.25O3-δ-Ce0.9Gd0.1O1.95 (LCM-CGO) nanocomposite layers with different LCM contents, between 40 and 60 wt %, are prepared in a single step by a spray-pyrolysis deposition method and evaluated as both air and fuel electrodes for solid oxide fuel cells (SOFCs). The formation of fluorite (CGO) and perovskite (LCM) phases in the nanocomposite electrode is confirmed by different structural and microstructural techniques. The intimate mixture of LCM and CGO phases inhibits the grain growth, retaining the nanoscale microstructure even after annealing at 1000 °C with a grain size lower than 50 nm for LCM-CGO compared to 200 nm for pure LCM. The synergetic effect of nanosized LCM and CGO by combining their high electronic and ionic conductivity, respectively, leads to efficient and durable symmetrical electrodes. The best electrochemical properties are found for 50 wt % LCM-CGO, showing polarization resistance values of 0.29 and 0.09 Ω cm2 at 750 °C in air and H2, respectively, compared to 2.05 and 1.9 Ω cm2 for a screen-printed electrode with the same composition. This outstanding performance is mainly ascribed to the nanoscale electrode microstructure formed directly on the electrolyte at a relatively low temperature. These results reveal that the combination of different immiscible phases with different crystal structures and electrochemical properties could be a promising strategy to design highly efficient and durable air and fuel electrodes for SOFCs.

Unraveling the Influence of the Electrolyte on the Polarization Resistance of Nanostructured La0.6Sr0.4Co0.2Fe0.8O3-δ Cathodes.

Large variations in the polarization resistance of La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) cathodes are reported in the literature, which are usually related to different preparation methods, sintering temperatures, and resulting microstructures. However, the influence of the electrolyte on the electrochemical activity and the rate-limiting steps of LSCF remains unclear. In this work, LSCF nanostructured electrodes with identical microstructure are prepared by spray-pyrolysis deposition onto different electrolytes: Zr0.84Y0.16O1.92 (YSZ), Ce0.9Gd0.1O1.95 (CGO), La0.9Sr0.1Ga0.8Mg0.2O2.85 (LSGM), and Bi1.5Y0.5O3-δ (BYO). The ionic conductivity of the electrolyte has a great influence on the electrochemical performance of LSCF due to the improved oxide ion transport at the electrode/electrolyte interface, as well as the extended ionic conduction paths for the electrochemical reactions on the electrode surface. In this way, the polarization resistance of LSCF decreases as the ionic conductivity of the electrolyte increases in the following order: YSZ > LSGM > CGO > BYO, with values ranging from 0.21 Ω cm2 for YSZ to 0.058 Ω cm2 for BYO at 700 °C. In addition, we demonstrate by distribution of relaxation times and equivalent circuit models that the same rate-limiting steps for the ORR occur regardless of the electrolyte. Furthermore, the influence of the current collector material on the electrochemical performance of LSCF electrodes is also analyzed.

Nanostructured BaCo0.4Fe0.4Zr0.1Y0.1O3-δ Cathodes with Different Microstructural Architectures.

Lowering the operating temperature of solid oxide fuel cells (SOFCs) is crucial to make this technology commercially viable. In this context, the electrode efficiency at low temperatures could be greatly enhanced by microstructural design at the nanoscale. This work describes alternative microstructural approaches to improve the electrochemical efficiency of the BaCo0.4Fe0.4Zr0.1Y0.1O3-δ (BCFZY) cathode. Different electrodes architectures are prepared in a single step by a cost-effective and scalable spray-pyrolysis deposition method. The microstructure and electrochemical efficiency are compared with those fabricated from ceramic powders and screen-printing technique. A complete structural, morphological and electrochemical characterization of the electrodes is carried out. Reduced values of area specific resistance are achieved for the nanostructured cathodes, i.e., 0.067 Ω·cm2 at 600 °C, compared to 0.520 Ω·cm2 for the same cathode obtained by screen-printing. An anode supported cell with nanostructured BCFZY cathode generates a peak power density of 1 W·cm-2 at 600 °C.

NH3/H2O-mediated proton conductivity and photocatalytic behaviour of Fe(ii)-hydroxyphosphonoacetate and M(ii)-substituted derivatives.

Synthesis redesign and derivatisation of Fe(ii)-hydroxyphosphonoacetate, incorporating different ammonia loads and M(ii) isomorphic substitutions (M = Mn, Co and Zn), have been implemented. The NH3 adsorption led to materials with enhanced proton conductivity, up to ∼10-3 S cm-1, although it caused a progressive amorphization. The Pair Distribution Function (PDF) analysis for this material confirmed the loss of crystallinity but the local order appeared to be maintained. The parent compound was shown to be an efficient photocatalyst for phenol, 4-chlorophenol and methylene blue even under mild conditions, with TOC removal of 75-90% at 50-150 min of reaction. The M(ii)-substituted derivatives displayed similar behaviour in properties, and therefore their multifunctional character, as the parent compound, although with slightly reduced capabilities.

Electrochemical stability of (La,Sr)CoO3-δ in (La,Sr)CoO3-δ/(Ce, Gd)O2-δ heterostructures.

A modulated coherent (La,Sr)CoO3-δ/(Ce,Gd)O2-δ heterostructure is characterized for the first time for its electronic and chemical properties. 2D-multilayer architectures are deposited on NdGaO3 (110) single crystal substrate by pulsed laser deposition, resulting in epitaxial structures with in-plane lattice rotation that, via the metal oxides' interfaces, induces mutual structural rearrangements. Our results show that (La,Sr)CoO3-d thin films of 10-100 nm are chemically unstable when exposed to air at 600 °C during electrical cyclic stress-tests. Conversely, improved stability is achieved confining LSC in the nanometric heterostructure. Remarkably, the chemical stabilization occurs without compromising substantially the electrical properties of the LSC component: the heterostructures show unexpected electrical behaviour with dominant electronic contributions, fast conductivity and mixed ionic-electronic properties, depending on the number of interfaces and the nano-scaled layers.

Effect of tri- and tetravalent metal doping on the electrochemical properties of lanthanum tungstate proton conductors.

Rare-earth tungstates (La(28-y)W(4+y)O(54+δ)□(2-δ)) have attracted attention recently because of their relatively high proton-electron conductivity and high stability in a CO2 environment. Since doping on the tungsten-site may increase the conductivity, a new series of compounds with composition La(5.5)W(1-x)M(x)O(11.25-δ) (M = Al, Ti and Zr; x = 0, 0.05 and 0.10) have been investigated. The crystal structure of these materials has been studied using X-ray and time-of-flight neutron powder diffraction by Rietveld analysis. The concentration of oxygen vacancies for hydration in the structure has been indirectly determined by thermogravimetric analysis, and the total conductivity in several pO2, pH2O and pD2O atmospheres has been studied by impedance spectroscopy. An increase in the conductivity is observed, ranging from 4.1 mS cm(-1) for the undoped sample to 9.2 mS cm(-1) for La(5.5)W(0.9)Ti(0.1)O(11.25-δ), in wet N2 at 800 °C.

Mechanism of stabilization of dicalcium silicate solid solution with aluminium.

Stoichiometric dicalcium silicate, Ca2SiO4, displays a well-known polymorphism with temperature. When this phase is doped by a range of elements, belite, one of the main phases of cements, is generated. Here, we thoroughly study the aluminum doping of dicalcium silicate. This type of study is important for cement characterization and also from a basic point of view. Ca2Si(1-2x)Al(2x)O(4-x)□(x) (x = 0, 0.010, 0.014, 0.03) has been prepared and studied by X-ray powder diffraction and the Rietveld method. The limiting composition has been established as Ca2Si0.972Al0.028O3.986□0.014. The (27)Al MAS NMR band located close to ~-70 ppm is ascribed to tetrahedral environments, in agreement with the proposed aliovalent Si/Al atomic substitution mechanism. Thermal analysis measurements under a wet atmosphere indirectly confirm the increase of oxygen vacancies as the amount of incorporated protons increases with the aluminium content. A thorough electrical characterization has been carried out including overall conductivity measurements under wet and dry atmospheres and conductivity as a function of the oxygen partial pressure. The samples show oxide anion conductivity with a small p-type electronic contribution under oxidizing conditions. These compounds display a very important proton contribution to the overall conductivities under humidified atmospheres.

Investigation into the effect of Si doping on the performance of Sr(1-y)Ca(y)MnO(3-δ) SOFC cathode materials.

In this paper we report the successful incorporation of silicon into Sr1-yCayMnO3-δ perovskite materials for potential applications in cathodes for solid oxide fuel cells. The Si substitution onto the B site of a (29)Si enriched Sr1-yCayMn1-xSixO3-δ perovskite system is confirmed by (29)Si MAS NMR measurements at low B0 field. The very large paramagnetic shift (~3000-3500 ppm) and anisotropy (span ~4000 ppm) suggests that the Si(4+) species experiences both Fermi contact and electron-nuclear dipolar contributions to the paramagnetic interaction with the Mn(3+/4+) centres. An improvement in the conductivity is observed for low level Si doping, which can be attributed to two factors. The first of these is attributed to the tetrahedral coordination preference of Si leading to the introduction of oxide ion vacancies, and hence a partial reduction of Mn(4+) to give mixed valence Mn. Secondly, for samples with high Sr levels, the undoped systems adopt a hexagonal perovskite structure containing face sharing of MnO6 octahedra, while Si doping is shown to help to stabilise the more highly conducting cubic perovskite containing corner linked octahedra. The level of Si, x, required to stabilise the cubic Sr1-yCayMn1-xSixO3-δ perovskite in these cases is shown to decrease with increasing Ca content; thus cubic symmetry is achieved at x = 0.05 for the Sr0.5Ca0.5Mn1-xSixO3-δ series; x = 0.075 for Sr0.7Ca0.3Mn1-xSixO3-δ; x = 0.10 for Sr0.8Ca0.2Mn1-xSixO3-δ; and x = 0.15 for SrMn1-xSixO3-δ. Composites with 50% Ce0.9Gd0.1O1.95 were examined on dense Ce0.9Gd0.1O1.95 pellets. For all series an improvement in the area specific resistances (ASR) values is observed for the Si-doped samples. Thus these preliminary results show that silicon can be incorporated into perovskite cathode materials and can have a beneficial effect on the performance.

Multifunctional lanthanum tetraphosphonates: flexible, ultramicroporous and proton-conducting hybrid frameworks.

A new flexible ultramicroporous solid, La(H(5)DTMP)·7H(2)O (1), has been crystallized at room temperature using the tetraphosphonic acid H(8)DTMP, hexamethylenediamine-N,N,N',N'-tetrakis(methylenephosphonic acid). Its crystal structure, solved by synchrotron powder X-ray diffraction, is characterised by a 3D pillared open-framework containing 1D channels filled with water. Upon dehydration, a new related crystalline phase, La(H(5)DTMP) (2) is formed. Partial rehydration of 2 led to La(H(5)DTMP)·2H(2)O (3). These new phases contain highly corrugated layers showing different degrees of conformational flexibility of the long organic chain. The combination of the structural study and the gas adsorption characterization (N(2) and CO(2)) suggests an ultramicroporous flexible framework. NO isotherms are indicative of a strong irreversible adsorption of NO within the pores. Impedance data indicates that 1 is a proton-conductor with a conductivity of 8 × 10(-3) S cm(-1) at 297 K and 98% of relative humidity, and an activation energy of 0.25 eV.

A new family of oxide ion conductors based on tricalcium oxy-silicate.

Tricalcium oxy-silicates, Ca3(SiO4)O and Ca2.93Mg0.07(Si0.98Al0.02O4)O0.99 [square]0.01, have been prepared as crystalline single phases. Ca3(SiO4)O and Ca2.93Mg0.07(Si0.98Al0.02O4)O0.99 [square]0.01 have triclinic and monoclinic structures, respectively. The samples show oxide anion conductivity with a small p-type electronic contribution under oxidizing conditions. At 1023 K, the oxide transport numbers range between 0.97 and 0.85 from reducing (dry 5%-H2-Ar/air gradient) to oxidizing (O2/air gradient) conditions in the 1023-1173 K interval. The thermal analyses showed a large weight loss on heating due to the presence of water in the materials. The monoclinic compound has ionic conductivities higher than those of the triclinic stoichiometric oxy-silicate, as expected due to the introduction of oxide vacancies. Typical total conductivities for these un-optimised solids are 10(-5)-10(-4) S cm(-1) at 1100 K. These compounds may contain a small amount of water, approximately 0.05 H2O moles per chemical formula, and they display an important proton contribution under a humidified atmosphere.